Supporting information

Size: px
Start display at page:

Download "Supporting information"

Transcription

1 Supporting information Diversity Oriented Asymmetric Catalysis (DOAC): Stereochemically Divergent Synthesis of Thiochromanes Using an Imidazoline-aminophenol aminophenol (IAP)-Ni Catalyzed Michael/Henry Reaction Takayoshi Arai, Yushi Yamamoto Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba , Japan S1

2 Contents 1. General S3 2. General procedure for tandem catalytic asymmetric thio Michael/Henry reaction and one pot reduction of nitro group S4 3. Optimization of catalytic Asymmetric thio Michael/Henry reaction S5 4. Reduction of the nitro group of the chiral thiochromanes S7 5. ESI MS analysis of IAP Ni thiolate complex S8 6. Plausible transition state model S9 7. Analytical data of (2S,3R,4R)- 2-aryl-3-nitrothiochroman-4-ols (6) S10 8. Analytical data of (2S,3R,4R)-3-amino-2-arylthiochroman-4-ols (7) S H NMR and 13 C NMR spectra of (2S,3R,4R)-3-nitro-2-arylthiochroman-4-ols (6) S H NMR and 13 C NMR spectra of (2S,3R,4R)-3-amino-2-arylthiochroman-4-ols (7) S42 S2

3 1. General Dry solvents were purchased from commercial suppliers and used without further purification. Analytical thin layer chromatography (TLC) was performed on glass plates coated with 0.25 mm mesh silica gel containing a fluorescent indicator (Merck, # ). Silica gel column chromatography was performed on Kanto silica gel 60 (spherical, µm). IR spectra were recorded on JASCO FT/IR 4100 using ATR. 1 H NMR spectra were recorded on JEOL ECS 400 (400MHz) or ECA 500 (500MHz) spectrometers. Chemical shifts of 1 H NMR spectra were reported relative to tetramethylsilane (δ 0) or Acetone d 6 (δ 2.05) or DMSO d 6 (δ 2.50). 13 C NMR spectra were recorded on JEOL ECA 400 (100MHz) or ECA 500 (125MHz) spectrometers. Chemical shifts of 13 C NMR spectra were reported relative to CDCl 3 (δ77.0) or Acetone d 6 (δ 29.8) or DMSO d 6 (δ 39.5). Splitting patterns were reported as s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad. General experimental details for synthesis of imidazoline aminophenol ligand (IAP) have been described. 1, 2 Mercaptobenzaldehydes (2-mercaptobenzaldehyde: ca. 75% purity, 5-(tert-butyl)-2-mercaptobenzaldehyde: ca. 86% purity, and 5-chloro-2-mercaptobenzaldehyde: ca. 93% purity) were synthesized according to known procedure. 3 [1] Arai, T.; Yokoyama, N.; Yanagisawa, A. Chem. Eur. J. 2008, 14, [2] Yokoyama, N.; Arai, T. Chem. Commun. 2009, [3] Toste, F. D.; Lough, A. J.; Still, W. J. Tetrahedron Lett. 1995, 36, S3

4 2. General procedure for tandem catalytic asymmetric thio Michael/Henry reaction and one pot reduction of nitro group IAP1 ( mmol) and Ni(OAc) 2 4H 2 O (0.015mmol) were added to a two necked round flask containing a stir bir under argon. Anhydrous MeOH (1 ml) was added to the flask and the mixture was stirred for 2 hours. After removal of the solvent under reduced pressure, anhydrous PhMe (1 ml) was added. To the resulting solution, nitroalkene (0.15 mmol) was added at room temperature and cooled to -40 C. Slow addition of 2-mercaptobenzaldehyde (0.225 mmol, ca. 75% purity) in anhydrous PhMe (5 ml) using syringe pump was conducted for 15 hours. After being stirred for appropriate time, the crude mixture was warmed to room temperature. (Procedure A for nitro compound) 0.6 ml of the crude reaction mixture was transferred into another flask via syringe and removed solvent under reduced pressure. Yield and diastereomeric ratio of the nitrothiochromane were determined by crude 1 H NMR. The crude mixture was purified by flash silica gel column chromatography to afford the 2 aryl 3 nitrothiochroman 4 ols. The enantiomeric excesses of the products were determined by chiral stationary phase HPLC using a Daicel Chiralpak AD H, OD H and IC 3 column. (Procedure B for aminoalcohol) After removal of the solvent of the resulting 5.4 ml of crude reaction mixture, dry MeOH (1.2 ml) was added at room temperature under argon. 2.7 mmol of Zn (nanopowder, purchased from Sigma Aldrich) was added. A mixture of 1N aq. HCl (810 µl) and AcOH (405 µl) was added to the heterogeneous solution and stirred for 30 minutes. Zn was filtered out and the filtrate was concentrated by rotary evaporator. CHCl 3 was added to the flask and neutralized by aq. NaHCO 3. The resulting mixture was extracted with CHCl 3 (10 ml x 3) and combined organic layer was dried over Na 2 SO 4. After removal of solvent under reduced pressure, diastereomeric ratio was determined by crude 1 H NMR. The crude mixture was purified by flash silica gel column chromatography to afford the 3 amino 2 arylthiochroman 4 ols. The enantiomeric excesses of the products were determined by chiral stationary phase HPLC using a Daicel Chiralpak AD H, AS H, IA, IC 3, Chiralcel OD H and OJ H column. S4

5 3. Optimization of reaction condition Table S1. Catalyst screening for thio Michael/Henry reaction. S5

6 Table S2. Solvent effect for thio Michael/Henry reaction. S6

7 4. Reduction of the nitro group of the chiral thiochromanes Table S3. Optimization of reduction of the nitro group S7

8 5. ESI MS analysis of IAP Ni thiolate complex H Ph Ph O Ni-IAP S Ts N N N Ni O S Br + H OHC IAP-Ni-thiolate Ph Br HRMScalcd.forC 45 H 40 Br 2 N 3 NiO 4 S 2 [M+H] + : found: m/z = Figure S1. ESI MS analysis of IAP Ni thiolate complex [IAP1 Ni thiolate + H] + species was observed in ESI MS. An ion peak at m/z = corresponds to the [IAP1 (phenoxide) Ni thiolate + H] +. S8

9 6. Plausible transition state model The formyl group of thiosalicylaldehyde would coordinate to the nickel center because Michael reaction of benzenethiol having no formyl group gave racemic product as shown in Scheme S1. (1.5 eq) SH IAP1(11mol%) Ni(OAc) 2 4H 2 O(10mol%) PhMe(0.025 M) -40 C,20h S Ph 8 86% yield <5%ee NO 2 Ph 5a NO 2 CHO 4a(1.5eq) SH IAP1(11mol%) Ni(OAc) 2 4H 2 O(10mol%) OH NO 2 PhMe(0.025 M) -40 C,16h Scheme S1. Effect of formyl group S Ph 6a >99% yield >99/1 dr 95%ee Figure S2. Plausible transition state model In TS2 (for all trans product), the diheadral angle between C=N and carbonyl C=O is narrow due to a strained thiochromane ring. TS1 having Ni containing chair like six-membered ring is favorable. S9

10 7. Analytical data of (2S,3R,4R)-2-aryl-3-nitro-thiochroman-4-ols (6) (2S,3R,4R) 3 nitro 2 phenylthiochroman 4 ol (6a) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to 0:1) as a yellow solid. 1 H NMR (500 MHz, Acetone d 6 ) δ (m, 2H), (m, 1H), (m, 2H), (m, 1H), 7.30 (dt, 1H, J = 7.8, 1.5 Hz), 7.20 (dt, 1H, J = 7.5, 1.2 Hz), 7.15 (dd, 1H, J = 8.1, 0.9 Hz), 5.70 (dd, 1H, J = 11.5, 2.9 Hz), (m, 2H), 5.31 (d, 1H, J = 11.8 Hz) ; 13 C NMR (100 MHz, Acetone d 6 ) δ 137.7, 134.6, 133.5, 132.0,129.9, 129.7, 129.3, 129.2, 125.7, 125.4, 90.2, 70.6, 41.4; HRMS calcd for C 15 H 13 NO 3 SNa [M+Na] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor 19.2 enantiomer t r = 15.1 min, major enantiomer t r = 22.6 min; 95% ee; [α] D = (c = 1.0, MeOH, 98/2 diastereomixture, 95% ee); IR (neat) 3417, 2957, 2925, 2854, 1550, 1315, 1034, 763, 698 cm -1. (2S,3R,4R) 2 (4 chlorophenyl) 3 nitrothiochroman 4 ol (6b) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (500 MHz, Acetone d 6 ) δ (m, 2H), 7.49 (dd, 1H, J = 7.7, 1.6 Hz), (m, 2H), 7.31 (dt, 1H, J = 7.7, 1.6 Hz), (m, 1H), (m, 1H), 5.70 (dd, 1H, J = 11.6, 2.9 Hz), 5.50 (br, 1H), 5.42 (br, 1H), 5.31 (d, 1H, J = 11.6 Hz); 13 C NMR (125 MHz, Acetone d 6 ) δ 136.8, 134.6, 134.4, 133.3, 132.2, 131.1, 130.1, 139.8, 125.8, 125.4, 89.9, 70.7, 40.6; HRMS calcd for C 15 H 11 NO 3 SCl [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 16.4 min, major enantiomer t r = 22.6 min; % ee; [α] D = (c = 0.1, MeOH, 96/4 diastereomixture, 94% ee); IR (neat) 3190, 2920, 1550, 1491, 1369, 1348, 1090, 1034, 1014, 768 cm -1. S10

11 (2S,3R,4R) 2 (3 chlorophenyl) 3 nitrothiochroman 4 ol (6c) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow amorphous. 1 H NMR (400 MHz, Acetone d 6 ) δ 7.71 (s, 1H), 7.59 (dd, 1H, J = 7.5, 1.1 Hz), 7.50 (d, 1H, J = 7.7 Hz), (m, 1H), (m, 1H), 7.21 (t, 1H, J = 7.5 Hz), 7.16 (d, 1H, J = 7.7 Hz), (m, 1H), 5.51 (br, 1H), 5.43 (br, 1H), 5.32 (d, 1H, J = 11.3 Hz); 13 C NMR (125 MHz, Acetone d 6 ) δ 140.4, 134.9, 134.4, 133.2, 132.2, 131.4, 130.1, 129.4, 129.3, 128.0, 125.8, 125.4, 89.7, 70.7, 40.8; HRMS calcd for C 15 H 11 NO 3 SCl [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak OD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 19.0 min, major enantiomer t r = min; 95% ee; [α] D = (c = 0.1, MeOH, 95/5 diastereomixture, 95% ee); IR (neat) 3420, 2921, 1550, 1476, 1366, 1090, 1036, 760, 733 cm -1. (2S,3R,4R) 2 (4 bromophenyl) 3 nitrothiochroman 4 ol (6d) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ 7.59 (s, 4H), 7.49 (dd, 1H, J = 7.8, 1.4 Hz), 7.31 (dt, 1H, J = 7.8, 1.4 Hz), 7.20 (dt, 1H, J = 7.6, 1.2 Hz), (m, 1H), 5.70 (dd, 1H, J = 11.7, 3.0 Hz), 5.50 (br, 1H), 5.42 (d, 1H, J = 2.5 Hz), 5.29 (d, 1H, J = 11.7 Hz); 13 C NMR (125 MHz, Acetone d 6 ) δ 137.3, 134.4, 133.2, 132.7, 132.2, 131.4, 130.0, 125.8, 125.3, 122.7, 89.8, 70.6, 40.6; HRMS calcd for C 15 H 11 NO 3 SBr [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak IC 3 column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor 24.4 enantiomer t r = 30.6 min, major enantiomer t r = 11.7 min; 93% ee; [α] D = (c = 0.1, MeOH, 97/3 diastereomixture, 93% ee); IR (neat) 3734, 1547, 1475, 1072, 1034, 1011, 765 cm -1. S11

12 (2S,3R,4R) 2 (3 bromophenyl) 3 nitrothiochroman 4 ol (6e) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a brown solid. 1 H NMR (500 MHz, Acetone d 6 ) δ (m, 1H), 7.64 (dt, 1H, J = 7.7, 1.2 Hz), (m, 1H), 7.50 (dd, 1H, J = 7.5, 1.4 Hz), 7.38 (t, 1H, J = 7.9 Hz), 7.31 (dt, 1H, J = 7.7, 1.4 Hz), 7.21 (dt, 1H, J = 7.5, 1.4 Hz), 7.16 (dd, 1H, J = 7.7, 1.2 Hz), (m, 1H), 5.49 (br, 1H), 5.43 (br, 1H), 5.30 (d, 1H, J = 11.5 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 137.7, 123.3, 132.1, 131.6, 131.4, , 89.6, 70.0, 40.4; HRMS calcd for C 15 H 11 NO 3 SBr [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = min, major enantiomer t r = 21.2 min; 94% ee; [α] D = (c = 0.1, MeOH, 97/3 diastreomixture, 94% ee); IR (neat) 3335, 2958, 1555, 1523, 1474, 1331, 1075, 1037, 768 cm -1. (2S,3R,4R) 2 (4 fluorophenyl) 3 nitrothiochroman 4 ol (6f) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a pale yellow amorphous. 1 H NMR (400 MHz, Acetone d 6 ) δ (m, 2H), 7.49 (dd, 1H, J = 7.7, 1.4 Hz), (m, 1H), (m, 4H), 5.68 (dd, 1H, J = 11.6, 2.9 Hz), 5.48 (br, 1H), 5.41 (d, 1H, J = 2.5 Hz), 5.31 (d, 1H, J = 11.6 Hz); 13 C NMR (100 MHz, Acetone d 6 ) δ (d, J = Hz), 134.4, (d, J = 2.9 Hz), 133.4, 132.1, (d, J = 8.6 Hz), 130.0, 125.7, 125.4, (d, J = 21.0 Hz), 90.1, 70.7, 40.5; HRMS calcd for C 15 H 11 NO 3 SF [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (95:5 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor enantiomer t r = 31.0 min, major enantiomer 25.8 t r = 37.6 min; 90% ee; [α] D = (c = 0.1, MeOH, 95/5 diastereomixture, 90% ee); IR (neat) 3734, 3419, 2924, 1552, 1508, 1315, 1227, 1035, 760 cm -1. S12

13 (2S,3R,4R) 3 nitro 2 (4 nitrophenyl)thiochroman 4 ol (6g) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to 0:1) as a yellow solid. 1 H NMR (500 MHz, Acetone d 6 ) δ (m, 2H), (m, 2H), (m, 1H), 7.32 (dt, 1H, J = 7.5, 1.4 Hz), 7.23 (dt, 1H, J = 7.5, 1.2 Hz), (m, 1H), (m, 1H), 5.60 (d, 1H, J = 5.2 Hz), (m, 2H); 13 C NMR (125 MHz, Acetone d 6 ) δ 148.8, 145.5, 134.4, 132.7, 132.3, 130.7, 130.2, 126.0, 125.3, 124.8, 89.5, 70.6, 40.6; HRMS calcd for C 15 H 11 NO 3 SCl [M+Cl] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (80:20 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 49.3 min, major enantiomer t r = 37.3 min; % ee; [α] D = (c = 0.2, MeOH, 91% ee); IR (neat) 3149, 3029, 2811, 1556, 1524, 1349, 1046, 764 cm -1. (2S,3R,4R) 3 nitro 2 (3 nitrophenyl)thiochroman 4 ol (6h) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ 8.55 (t, 1H, J = 2.0 Hz), (m, 1H), 8.12 (d, 1H, J = 7.7 Hz), (m, 1H), (m, 1H), 7.33 (dt, 1H, J = 7.7, 1.4 Hz), 7.23 (dt, 1H, J = 7.5, 1.1 Hz), 7.19 (d, 1H, J = 7.7 Hz), 5.90 (dd, 1H, J = 11.6, 2.9 Hz), 5.59 (d, 1H, J = 5.0 Hz), (m, 2H); 13 C NMR (100 MHz, Acetone d 6 ) δ149.4, 140.4, 135.9, 134.4, 133.7, 132.8, 132.3, 131.1, 130.2, 125.9, 125.3, 124.2, 89.5, 70.7, 40.6; HRMS calcd for C 15 H 12 N 2 O 5 SCl [M+Cl] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak IA column (90:10 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor enantiomer t r = min, major enantiomer t r = 44.1 min; 92% ee; [α] D = (c = 0.1, MeOH, 97/3 diastereomixture, 93% ee); IR (neat) 3734, 3649, 3361, 3195, 2921, 2851, 1554, 1527, 1350, 1037, 758, 686 cm -1. S13

14 (2S,3R,4R) 2 (4 methoxyphenyl) 3 nitrothiochroman 4 ol (6i) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to 0:1) as a yellow solid. 1 H NMR (500 MHz, Acetone d 6 ) δ (m, 2H), 7.47 (dd, 1H, J = 7.8, 1.5 Hz), 7.29 (dt, 1H, J = 7.5, 1.4 Hz), 7.19 (dt, 1H, J = 7.5, 1.2 Hz), 7.14 (dd, 1H, J = 8.0, 1.2 Hz), (m, 2H), 5.62 (dd, 1H, J = 11.5, 2.9 Hz), (m, 2H), 5.25 (d, 1H J = 11.8 Hz), 3.79 (s, 3H); 13 C NMR (125 MHz, Acetone d 6 ) δ 160.7, 134.5, 133.9, 132.1, 130.5, 129.9, 129.2, 125.6, 125.4, 115.0, 90.4, 70.8, 55.5, 40.9; HRMS calcd for C 16 H 14 NO 4 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor 26.6 enantiomer t r = 22.5 min, major enantiomer t r = 35.4 min; 84% ee; [α] D = (c = 0.2, MeOH, 95/5 diastereomixture, 84% ee); IR (neat) 2927, 1558, 1513, 1308, 1255, 1176, 1033, 757 cm -1. (2S,3R,4R) 2 (3 methoxyphenyl) 3 nitrothiochroman 4 ol (6j) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ 7.48 (dd, 1H, J = 7.7, 1.4 Hz), (m, 2H), 7.20 (dd, 1H, J = 7.5, 1.4 Hz), (m, 3H), (m, 1H), (m, 1H), 5.48 (br, 1H), 5.40 (br, d, 1H, J = 2.7 Hz), 5.25 (d, 1H, J = 11.6 Hz), 3.82 (s, 3H); 13 C NMR (100 MHz, Acetone d 6 ) δ 160.9, 139.3, 134.5, 133.7, 132.1, 130.7, 130.0, 125.7, 125.4, 121.4, 114.9, 114.7, 90.0, 70.7, 55.6, 41.4; HRMS calcd for C 16 H 14 NO 4 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = min, major enantiomer t r = 39.3 min; 92% ee; [α] D = (c = 1.0, MeOH, 98/2 diastereomixture, 94% ee); IR (neat) 2926, 1551, 1317, 1261, 1035, 756 cm -1. S14

15 (2S,3R,4R) 3 nitro 2 (p tolyl)thiochroman 4 ol (6k) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to 0:1) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ (m, 3H), 7.29 (dt, 1H, J = 7.5, 1.4 Hz), (m, 3H), 7.14 (dd, 1H, J = 7.9, 1.1 Hz), 5.66 (dd, 1H, J = 11.6, 2.9 Hz), (br, 2H), 5.24 (d, 1H, J = 11.6 Hz), 2.32 (s, 3H); 13 C NMR (100 MHz, Acetone d 6 ) δ139.1, 134.6, 134.5, 133.8, 132.1, 130.3, 130.0, 129.2, 125.6, 125.4, 90.3, 70.7, 41.1, 21.1; HRMS calcd for C 16 H 14 NO 3 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (80:20 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r =11.3 min, 20.3 major enantiomer t r = 19.0 min; 84% ee; [α] D = (c = 0.1, MeOH, 91/9 diastereomixture, 84% ee); IR (neat) 2919, 1552, 1474, 1369, 1035, 760 cm -1. (2S,3R,4R) 3 nitro 2 (m tolyl)thiochroman 4 ol (6l) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as an orange amorphous. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 4H), (m, 3H), (m, 3H), 2.88 (br, 1H), 2.35 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 138.7, 135.2, 132.9, 131.7, 130.8, (2C), 129.1, 128.8, 125.4, 125.5, 125.4, 89.9, 70.0, 41.0, 21.3; HRMS calcd for C 16 H 14 NO 3 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (90:10 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 19.1 min, major enantiomer t r = 29.1 min; 94% ee; [α] D = (c = 0.1, MeOH, 96/4 diastereomixture, 94% ee); IR (neat) 3158, 1557, 1520, 1317, 1038, 760 cm -1. S15

16 (2R,3R,4R) 3 nitro 2 (thiophen 2 yl)thiochroman 4 ol (6m) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ (m, 2H), (m, 1H), (m, 1H), 7.21 (dt, 1H, J = 7.5, 1.4 Hz), (m, 1H), 7.04 (dd, 1H, J = 5.2, 1.6 Hz), 5.61 (d, 1H, J = 11.4 Hz), 5.54 (dd, 1H, J = 11.2, 2.8 Hz), 5.48 (br, 1H), 5.38 (d, 1H, J = 2.8 Hz); 13 C NMR (100 MHz, Acetone d 6 ) δ 140.3, 134.4, 133.3, 131.8, 130.0, 128.6, 128.0, 127.2, 125.9, 125.4, 91.8, 70.8, 37.3; HRMS calcd for C 13 H 10 NO 3 S 2 [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (85:15 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor enantiomer t r = 12.1 min, major enantiomer t r = 15.4 min; % ee; [α] D = (c = 0.1, MeOH, 91/9 diastereomixture, 94% ee); IR (neat) 2922, 1552, 1518, 1315, 1077, 1032, 757, 733 cm -1. (2S,3R,4R) 6 chloro 3 nitro 2 phenylthiochroman 4 ol (6n) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow solid. 1 H NMR (400 MHz, Acetone d 6 ) δ (m, 2H), 7.56 (d, 1H, J = 2.2 Hz), (m, 4H), 7.21 (d, 1H, J = 8.7 Hz), 5.75 (dd, 1H, J = 11.2, 3.1 Hz), 5.65 (br, 1H), 5.43 (d, 1H, J = 2.5 Hz), 5.26 (d, 1H, J = 11.4 Hz); 13 C NMR (100 MHz, Acetone d 6 ) δ 137.5, 136.7, 132.7, 131.4, 130.7, 129.9, 129.8, 129.5, 129.3, 127.3, 90.1, 70.2, 42.0; HRMS calcd for C 15 H 11 NO 3 SCl [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (85:15 hexane : 2 propanol, 0.5 ml/min, 254 nm); minor 25.0 enantiomer t r = 25.2 min, major enantiomer t r = 27.4 min; 80% ee; [α] D = (c = 0.1, MeOH, 84/16 diastereomixture, 80% ee); IR (neat) 3734, 3649, 2923, 2852, 1556, 1456, 1362, 1102, 696 cm -1. S16

17 (2S,3R,4R) 6 (tert butyl) 3 nitro 2 phenylthiochroman 4 ol (6o) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to AcOEt) as a yellow amorphous. 1 H NMR (400 MHz, Acetone d 6 ) δ (m, 2H), 7.55 (d, 1H, J = 2.0 Hz), (m, 4H), (m, 1H), (m, 1H), 5.41 (br, 2H), 5.28 (d, 1H, J = 11.7 Hz), 1.32 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ) δ 148.6, 135.4, 131.0, 129.4, 129.1, 129.0, 128.9, 128.5, 128.1, 127.7, 127.4, 125.0, 90.2, 70.5, 40.9, 34.4, 31.2; HRMS calcd for C 19 H 20 NO 3 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (90:10 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 18.4 min, major enantiomer t r = 14.2 min; 87% ee; [α] D = (c = 0.1, MeOH, 91/9 diastereomixture, 87% ee); IR (neat) 3735, 3649, 2962, 2904, 1556, 1485, 1457, 1361, 697 cm -1. (2S,3R,4R) 3 nitro 2 pentylthiochroman 4 ol (6p) According to the general procedure A, the title compound was obtained by silica gel column chromatography (Hexane : CHCl 3 = 1:1 to 0:1) as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 3H), 5.14 (s, 1H), 4.86 (dd, 1H, J = 9.5, 2.6 Hz), 4.13 (dt, 1H, J = 9.5, 4.0 Hz), 2.98 (d, 1H, J = 4.9 Hz), (m, 8H), (m, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 129.6, 129.5, 128.5, 126.6, 125.3, 90.2, 69.7, 38.0, 32.6, 31.2, 25.7, 22.3, 13.9; HRMS calcd for C 14 H 18 NO 3 S [M H] : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (95:5 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 20.0 min, major enantiomer t r = 32.9 min; 4% ee; IR (neat) 3734, 3649, 3393, 2955, 2927, 2857, 1556, 1456, 1375, 1079, 1038, 750, 696 cm -1. S17

18 8. Analytical data of (2S,3R,4R)-3-amino-2-arylthiochroman-4-ols (7) (2S,3R,4R) 3 amino 2 phenylthiochroman 4 ol (7a) According to the general procedure B, the title compound was obtained by silica gel column chromatography (AcOEt to CHCl 3 : MeOH = 10:1) as a white solid. 1 H NMR (500 MHz, DMSO d 6 ) δ (m, 2H), 7.39 (t, 2H, J = 7.5 Hz), (m, 2H), 7.18 (dt, 1H, J = 7.5, 1.4 Hz), (m, 2H), 4.55 (d, 1H, J = 2.6 Hz), 4.43 (d, 1H, J = 10.0 Hz), 3.31 (dd, 1H, J = 10.0, 2.6 Hz); 13 C NMR (125 MHz, DMSO d 6 ) δ 139.0, 136.2, 133.1, 131.2, 129.2, 128.7, 128.1, 127.8, 124.4, 123.9, 69.7, 54.8, 46.0; HRMS calcd for C 15 H 16 NOS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column and Chiralcel OD H column (90:10 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 50.9 min, major enantiomer t r = 43.9 min; 96% ee; [α] D = (c = 1.0, MeOH, 96% ee); IR (neat) 3734, 3649, 3134, 2878, 1560, 1472, 1104, 1078, 872, 698 cm -1. (2S,3R,4R) 3 amino 2 (4 chlorophenyl)thiochroman 4 ol (7b) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a white solid. 1 H NMR (500 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), (m, 2H), 4.69 (d, 1H, J = 2.6 Hz), 4.44 (d, 1H, J = 9.7 Hz), 3.50 (d, 1H, J = 8.6 Hz), 2.04 (br, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 136.6, 134.1, 134.0, 133.3, 131.2, 130.3, 129.2, 128.8, 125.2, 124.7, 70.0, 55.3, 46.1; HRMS calcd for C 15 H 15 NOSCl [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (97.5 : 2.5 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor enantiomer t r = 62.4 min, major enantiomer t r = 38.8 min; % ee; [α] D = (c = 0.5, MeOH, 95% ee); IR (neat) 3734, 3649, 3375, 3066, 2875, 1490, 1088, 1012, 849, 752 cm -1. S18

19 (2S,3R,4R) 3 amino 2 (3 chlorophenyl)thiochroman 4 ol (7c) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a pale yellow solid. 1 H NMR (400 MHz, DMSO d 6 ) δ 7.51 (s, 1H), (m, 3H), 7.32 (d, 1H, J = 7.5 Hz), 7.19 (dt, 1H, J = 7.7, 1.4 Hz), (m, 2H), 4.53 (d, 1H, J = 2.5 Hz), 4.45 (d, 1H, J = 10.2 Hz), 3.32 (dd, 1H, J = 10.2 H; 13 C NMR (100 MHz, DMSO d 6 ) δ 141.9, 136.2, 133.1, 132.7, 131.1, 130.4, 129.0, 128.2, 128.0, 127.7, 124.3, 124.0, 69.9, 54.6, 45.6; HRMS calcd for C 15 H 15 NOSCl [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H and AS H column (93 : 7 hexane : 2 propanol, ml/min, 254 nm); minor enantiomer t r = 63.6 min, major enantiomer t r = 43.3 min; 98% ee; [α] D = (c = 0.25, MeOH, 98% ee); IR (neat) 3734, 3649, 3374, 3055, 2920, 2850, 1568, 1106, 1076, 780, 754 cm -1. (2S,3R,4R) 3 amino 2 (4 bromophenyl)thiochroman 4 ol (7d) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a white crystalline solid. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.39 (d, 1H, J = 7.6 Hz), (m, 2H), (m, 1H), (m, 2H), 4.69 (d, 1H, J = 2.9 Hz), 4.43 (d, 1H, J = 9.7 Hz), 3.50 (dd, 1H, J = 9.7, 2.7 Hz), 1.95 (br, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 137.2, 134.0, 133.3, 132.2, 131.1, 130.7, 128.8, 125.2, 124.7, 122.3, 70.0, 55.3, 46.2; HRMS calcd for C 15 H 15 NOSBr [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (90 : 10 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 19.5 min, major enantiomer t r = 14.8 min; 93% ee; [α] D = (c = 0.25, MeOH, 93% ee); IR (neat) 3734, 3649, 3375, 3065, 2875, 1569, 1486, 1472, 1071, 1009, 793, 752, 728 cm -1. S19

20 (2S,3R,4R) 3 amino 2 (3 bromophenyl)thiochroman 4 ol (7e) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a white solid. 1 H NMR (500 MHz, DMSO d 6 ) δ 7.65 (t, 1H, J = 1.7 Hz), (m, 1H), 7.47 (d, 1H, J = 8.0 Hz), (m, 2H), 7.19 (dt, 1H, J = 7.7, 1.4 Hz), (m, 2H), 5.56 (br, 1H), 4.53 (br, 1H), 4.44 (d, 1H, J = 10.0 Hz), (m, 1H), 1.48 (br, 2H); 13 C NMR (125 MHz, DMSO d 6 ) δ 142.2, 136.2, 132.7, 131.8, 131.1, 130.7, 130.6, 128.3, 128.1, 124.3, 124.0, 121.7, 69.9, 54.6, 45.5; HRMS calcd for C 15 H 15 NOSBr [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AD H column (95 : 5 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = min, major enantiomer t r = 30.8 min; 98% ee; [α] D = (c = 0.1, MeOH, 98% ee); IR (neat) 3734, 3649, 3369, 3053, 2894, 2841, 1566, 1471, 1324, 1073, 1011, 919, 779, 756, 687 cm -1 (2S,3R,4R) 3 amino 2 (4 fluorophenyl)thiochroman 4 ol (7f) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a yellow solid. 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), 7.40 (d, 1H, J = 7.7 Hz), (m, 1H), (m, 4H), 4.71 (d, 1H, J = 2.9 Hz), 4.46 (d, 1H, J = 9.7 H), (m, 1H), 2.02 (br, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 134.0, 133.5, 131.2, 130.7, 130.6, 128.8, 125.3, 124.7, 116.1, 115.9, 70.1, 55.5, 46.0; HRMS calcd for C 15 H 15 N 2 OSF [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (97.5 : 2.5 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor 25.8 enantiomer t r = 55.4 min, major enantiomer t r = 35.6 min; 92% ee; [α] D = (c = 0. 5, MeOH, 92% ee); IR (neat) 3734, 3649, 3384, 2924, 2880, 2852, 1599, 1507, 1473, 1212, 1159, 1108, 856, 789, 757 cm -1 S20

21 (2S,3R,4R) 3 amino 2 (4 methoxyphenyl)thiochroman 4 ol (7g) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as pale a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), (m, 1H), (m, 2H), 6.91 (d, 2H, J = 8.6 Hz), 4.72 (d, 1H, J = 2.0 Hz), 4.42 (d, 1H, J = 10.0 Hz), 3.82 (s, 3H), 3.49 (dd, 1H, J = 10.0, 2.5 Hz), 2.37 (br, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.5, 134.2, 133.9, 131.3, 130.1, 129.5, 128.6, 125.2, 124.4, 70.1, 55.3, 45.6, 29.7; HRMS calcd for C 16 H 18 NO 2 S [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OJ H column (90 : 10 hexane : 2 propanol, 1.0 ml/min, 254 nm); minor enantiomer t r = 31.7 min, major enantiomer t r = 22.9 min; % ee; [α] D = (c = 0.25, MeOH, 83% ee); IR (neat) 3734, 3649, 2901, 2834, 1608, 1509, 1249, 1175, 1028, 754, 731 cm -1 (2S,3R,4R) 3 amino 2 (3 methoxyphenyl)thiochroman 4 ol (7h) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a slightly yellow solid. 1 H NMR (500 MHz, DMSO d 6 ) δ (m, 2H), 7.18 (dt, 1H, J = 7.5, 1.4 Hz), (m, 2H), (m, 2H), 4.54 (d, 1H, J = 2.3 Hz), 4.40 (d, 1H, J = 10.0 Hz), 3.76 (s, 3H), 3.32 (br, 3H), (m, 1H); 13 C NMR (125 MHz, DMSO d 6 ) δ 159.4, 140.6, 136.1, 133.1, 131.2, 129.8, 128.1, 124.4, 123.9, 121.3, 114.7, 113.3, 69.7, 55.1, 54.8, 46.1; HRMS calcd for C 16 H 18 NO 2 S [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel AS H column (95 : 5 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 78.0 min, major enantiomer t r = min; 99% ee; [α] D = (c = 0.25, MeOH, 99% ee); IR (neat) 3739, 3649, 3370, 2955, 2917, 2851, 1596, 1490, 1469, 1265, 1161, 775, 755 cm -1 S21

22 (2S,3R,4R) 3 amino 2 (p tolyl)thiochroman 4 ol (7i) According to the general procedure B, the title compound was obtained by silica gel column chromatography (AcOEt to CHCl 3 : MeOH = 5:1) as a slightly yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.39 (d, 1H, J = 7.4 Hz), 7.33 (d, 2H, J = 8.1 Hz), 7.19 (d, 3H, J = 7.4 Hz), (m, 2H), 4.72 (d, 1H, J = 2.5 Hz), 4.43 (d, 1H, J = 10.1 Hz), (m, 1H), 2.48 (br, 3H), 2.36 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 138.2, 134.8, 134.1, 133.9, 131.2, 129.7, 128.9, 128.7, 125.2, 124.5, 70.1, 55.4, 46.2, 21.1; HRMS calcd for C 16 H 18 NOS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OJ H column (90 : 10 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 32.7 min, major enantiomer t r = 20.2 min; 91% ee; [α] D = (c = 0.25, MeOH, 91% ee); IR (neat) 3734, 3649, 3377, 2918, 1510, 775, 754 cm -1 (2S,3R,4R) 3 amino 2 (m tolyl)thiochroman 4 ol (7j) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane : AcOEt = 2:1 to CHCl 3 : MeOH = 5:1) as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 38 (d, 1H, J = 7.5 Hz), (m, 3H), (m, 1H), (m, 3H), 4.74 (s, 1H), 4.42 (d, 1H, J = 10.0 Hz), 3.55 (d, 1H, J = 9.7 Hz), 2.81 (br, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 138.7, 137.8, 134.1, 133.8, 131.2, 129.7, 129.1, 128.9, 128.7, 126.1, 125.2, 124.5, 70.2, 55.4, 46.5, 21.4; HRMS calcd for C 16 H 17 NOS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel IC 3 and AD H column (95 : 5 hexane : 2 propanol, 0.6 ml/min, nm); minor enantiomer t r = 98.1 min, major enantiomer t r = 62.7 min; >99% ee; [α] D = (c = 0.25, MeOH, >99% ee); IR (neat) 3734, 3649, 3375, 2987, 2891, 1568, 1470, 1075, 1013, 768, 753 cm -1 S22

23 (2R,3R,4R) 3 amino 2 (thiophen 2 yl)thiochroman 4 ol (7k) According to the general procedure B, the title compound was obtained by silica gel column chromatography (hexane : AcOEt = 2:1 to CHCl 3 : MeOH = 5:1) as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.38 (d, 1H, J = 7.7 Hz), 7.32 (dd, 1H, J = 5.2, 0.9 Hz), (m, 1H), (m, 3H), (m, 1H), 4.77 (d, 1H, J = 9.5 Hz), 4.72 (d, 1H, J = 2.7 Hz), 3.45 (dd, 1H, J = 9.5, 2.7 Hz), 2.28 (br, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 141.8, 133.9, 133.2, 131.1, 128.7, 127.4, 127.0, 126.1, 125.1, 124.7, 70.0, 56.8, 42.5; HRMS calcd for C 13 H 14 NOS 2 [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OJ H column (85 : 15 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor 24.8 enantiomer t r = 21.4 min, major enantiomer t r = 15.4 min; 97% ee; [α] D = (c = 0.25, MeOH, 95/5 dr, 97% ee); IR (neat) 3734, 3649, 3374, 3083, 2879, 1574, 1472, 1425, 1105, 754, 722, 700 cm -1 (2S,3R,4R) 3 amino 2 (4 aminophenyl)thiochroman 4 ol (7l) According to the general procedure B, the title compound was obtained by silica gel column chromatography (AcOEt to CHCl 3 : MeOH = 5:1) as a yellow solid. 1 H NMR (400 MHz, DMSO d 6 ) δ (m, 1H), 7.16 (dt, 1H, J = 7.8, 1.6 Hz), (m, 4H), 6.55 (d, 2H, J = 8.6 Hz), 5.13 (br, 2H), 4.55 (d, 1H, J = 2.5 Hz), 4.26 (d, 1H, J = 10.4 Hz), 3.50 (br, 1H), 3.42 (br, 2H), 3.19 (dd, 1H, J = 10.2, 2.5 Hz); 13 C NMR (100 MHz, DMSO d 6 ) δ 148.4, 136.1, 134.0, 131.3, 129.7, 128.0, 124.6, 124.3, 123.7, 114.0, 69.7, 55.1, 45.6; HRMS calcd for C 15 H 17 N 2 OS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (70 : 30 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 43.2 min, major enantiomer t r = 18.4 min; 92% ee; [α] D = (c = 0.125, MeOH, 92% ee); IR (neat) 3734, 3649, 2919, 1619, 1516, 1474, 1289, 1270, 1010, 759, 728 cm -1 S23

24 (2S,3R,4R) 3 amino 2 (3 aminophenyl)thiochroman 4 ol (7m) According to the general procedure B, the title compound was obtained by silica gel column chromatography (AcOEt to CHCl 3 : MeOH = 5:1) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.38(d, 1H, J = 7.4 Hz), (m, 4H), 6.82 (d, 1H, J = 7.9 Hz), (m, 1H), (m, 1H), 4.73 (d, 1H, J = 2.7 Hz), 4.36 (d, 1H, J = 10.1 Hz), 3.51 (dd, 1H, J = 9.9, 2.7 Hz), 3.34 (br) 2.03 (br); 13 C NMR (100 MHz, CDCl 3 ) δ 147.0, 138.6, 134.0, 133.6, 131.4, 130.0, 128.6, 125.2, 124.5, 119.0, 115.4, 115.1, 69.5, 55.4, 45.9; HRMS calcd for C 15 H 17 N 2 OS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (70 : 30 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 20.9 min, major enantiomer t r = min; 87% ee; [α] D = (c = 0.025, MeOH, 87% ee); IR (neat) 3734, 3649, 3348, 3214, 2923, 1604, 1458, 1297, 1262, 1074, 754, 731, 698 cm -1 (2S,3R,4R) 3 amino 6 (tert butyl) 2 phenylthiochroman 4 ol (7n) According to the general procedure B, the title compound was obtained by silica gel column chromatography ((hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 10:1) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (d, 2H, J = 7.0 Hz), (m, 4H), (m, 1H), 7.07 (d, 1H, J = 8.3 Hz), 4.71 (d, 1H, J = 2.0 Hz), 4.44 (d, 1H, J = 9.9 Hz), 3.53 (d, 1H, J = 9.0 Hz), 2.30 (br, 3H), 1.31 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ) δ 147.6, 138.0, 133.6, 130.2, , , 128.3, 128.1, 126.1, 124.9, 70.3, 55.6, 46.4, 34.3, 31.2; HRMS calcd for C 19 H 24 NOS [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralpak AS H column (95 : 5 hexane : 2 propanol, 0.7 ml/min, 254 nm); minor enantiomer t r = 23.1 min, major enantiomer t r = 18.5 min; % ee; [α] D = (c = 0.5, MeOH, 92% ee); IR (neat) 3734, 3649, 3289, 2960, 2901, 1576, 1484, 1455, 1013, 819, 741, 698 cm -1 S24

25 (2S,3R,4R) 3 amino 6 chloro 2 phenylthiochroman 4 ol (7o) According to the general procedure B, the title compound was obtained by silica gel column chromatography ((hexane: AcOEt = 2:1 to CHCl 3 : MeOH = 5:1) as an orange amorphous. 1 H NMR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 2H), (m, 1H), 7.18 (dd, 1H, J = 8.6, 2.3 Hz), 7.09 (d, 1H, J = 8.3 Hz), 4.63 (d, 1H, J = 2.6 Hz), 4.40 (d, 1H, J = 9.5 Hz), (m, 1H), 2.18 (br, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 137.7, 135.9, 132.1, 130.7, 130.0, 129.1, 128.9, 128.6, 128.4, 126.6, 69.2, 55.3, 47.1; HRMS calcd for C 15 H 14 NOSCl [M+H] + : , found: m/z ; Enantiomeric excess was determined by HPLC with a Chiralcel OD H column (80 : 20 hexane : 2 propanol, 0.7 ml/min, nm); minor enantiomer t r = 9.0 min, major enantiomer t r = 7.9 min; 84% ee; [α] D = (c = 0.25, MeOH, 90/10 dr, 84% ee); IR (neat) 3734, 3649, 3287, 2902, 1455, 1101, 1024, 810, 736, 698 cm -1 S25

26 9. 1 H NMR and 13 C NMR spectra of (2S,3R,4R)-3-nitro-2-arylthiochroman-4-ols (6) S26

27 S27

28 S28

29 S29

30 S30

31 S31

32 S32

33 S33

34 S34

35 S35

36 S36

37 S37

38 S38

39 S39

40 S40

41 S41

42 10. 1 H NMR and 13 C NMR spectra of (2S,3R,4R)-3-amino-2-arylthiochroman-4-ols (7) S42

43 S43

44 S44

45 S45

46 S46

47 S47

48 S48

49 S49

50 S50

51 S51

52 S52

53 S53

54 S54

55 S55

56 S56

p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of

p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of Supporting Information for: p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN 3 for Synthesis of 4-Aryl-NH-1,2,3-triazoles Xue-Jing Quan, Zhi-Hui Ren, Yao-Yu Wang, and

More information

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 Organocatalytic Asymmetric Sulfa-Michael Addition to α,β- Unsaturated Ketones Paolo Ricci, Armando Carlone, Giuseppe

More information

Masatoshi Shibuya,Takahisa Sato, Masaki Tomizawa, and Yoshiharu Iwabuchi* Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences,

Masatoshi Shibuya,Takahisa Sato, Masaki Tomizawa, and Yoshiharu Iwabuchi* Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Oxoammonium ion/naclo 2 : An Expedient, Catalytic System for One-pot Oxidation of Primary Alcohols to Carboxylic Acid with Broad Substrate Applicability Masatoshi Shibuya,Takahisa Sato, Masaki Tomizawa,

More information

Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature

Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature Supplementary Information Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature Weili Si 1, Xuan Zhang 1, Shirong Lu 1, Takeshi Yasuda

More information

SUPPORTING INFORMATION

SUPPORTING INFORMATION SUPPORTING INFORMATION Exploiting the Ring Strain in Bicyclo[2.2.1]heptane Systems for the Stereoselective Preparation of Highly Functionalized Cyclopentene, Dihydrofuran, Pyrroline and Pyrrolidine Scaffolds

More information

Rameshwar Prasad Pandit and Yong Rok Lee * School of Chemical Engineering, Yeungnam University, Gyeongsan , Korea

Rameshwar Prasad Pandit and Yong Rok Lee * School of Chemical Engineering, Yeungnam University, Gyeongsan , Korea Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Novel ne-pot Synthesis of Diverse γ,δ-unsaturated β-ketoesters by Thermal

More information

Copyright Wiley-VCH Verlag GmbH, D Weinheim, Angew. Chem

Copyright Wiley-VCH Verlag GmbH, D Weinheim, Angew. Chem Copyright Wiley-VCH Verlag GmbH, D-69451 Weinheim, 2000. Angew. Chem. 2000. Supporting Information for Salen as Chiral Activator : Anti vs Syn Switchable Diastereoselection in the Enantioselective Addition

More information

Regioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation

Regioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation Regioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation Qingshan Tian, Xianmin Chen, Wei Liu, Zechao Wang, Suping Shi, Chunxiang Kuang,* Department of Chemistry, Tongji University,

More information

Lewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines

Lewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines Supporting Information for Lewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines Yingle Liu a, Jiawang Liu

More information

Preparation of Stable Aziridinium Ions and Their Ring Openings

Preparation of Stable Aziridinium Ions and Their Ring Openings Supplementary Information Preparation of Stable Aziridinium Ions and Their Ring Openings Yongeun Kim a Hyun-Joon Ha*, a Sae Young Yun b and Won Koo Lee,*,b a Department of Chemistry and Protein Research

More information

Stereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines

Stereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines Stereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines Toni Moragas Solá, a Ian Churcher, b William Lewis a and Robert A. Stockman* a Supplementary Information

More information

Supporting Information

Supporting Information Supporting Information Asymmetric Catalysis of the Carbonyl-Amine Condensation: Kinetic Resolution of Primary Amines Sayantani Das, Nilanjana Majumdar, Chandra Kanta De, Dipti Sankar Kundu, Arno Döhring,

More information

Enantioselective synthesis of anti- and syn-β-hydroxy-α-phenyl carboxylates via boron-mediated asymmetric aldol reaction

Enantioselective synthesis of anti- and syn-β-hydroxy-α-phenyl carboxylates via boron-mediated asymmetric aldol reaction Enantioselective synthesis of anti- and syn-β-hydroxy-α-phenyl carboxylates via boron-mediated asymmetric aldol reaction P. Veeraraghavan Ramachandran* and Prem B. Chanda Department of Chemistry, Purdue

More information

Synthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice

Synthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice Supporting Information Rec. Nat. Prod. 9:4 (2015) 561-566 Synthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice Anita Mahapatra 1*, Purvi Shah 1, Mehul Jivrajani

More information

Chiral Squaramide Derivatives are Excellent Hydrogen Bond Donor Catalysts. Jeremiah P. Malerich, Koji Hagihara, and Viresh H.

Chiral Squaramide Derivatives are Excellent Hydrogen Bond Donor Catalysts. Jeremiah P. Malerich, Koji Hagihara, and Viresh H. Chiral Squaramide Derivatives are Excellent ydrogen Bond Donor Catalysts Jeremiah P. Malerich, Koji agihara, and Viresh. Rawal* Department of Chemistry, University of Chicago, Chicago, Illinois 60637 E-mail:

More information

Supporting Information

Supporting Information Supporting Information De Novo Synthesis of Polysubstituted Naphthols and Furans Using Photoredox Neutral Coupling of Alkynes with 2-Bromo-1,3-Dicarbonyl Compounds Heng Jiang, Yuanzheng Cheng, Yan Zhang,*

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Enantioselective Rhodium-catalyzed Addition of Arylboronic Acids to α-ketoesters Hai-Feng Duan, Jian-Hua Xie, Xiang-Chen Qiao, Li-Xin Wang,

More information

Supporting Information. An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization

Supporting Information. An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization Supporting Information An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization Michiaki, Kawahara, Atsushi Nishida, Masako Nakagawa* Faculty of Pharmaceutical

More information

Divergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes

Divergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes Divergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes Serena Mantenuto, Fabio Mantellini, Gianfranco Favi,* and Orazio A. Attanasi Department of Biomolecular

More information

Supporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylin

Supporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylin Supporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylindoles Wei-Li Chen, Si-Yi Wu, Xue-Ling Mo, Liu-Xu Wei,

More information

Zinc Chloride Promoted Formal Oxidative Coupling of Aromatic Aldehydes and Isocyanides to α- Ketoamides

Zinc Chloride Promoted Formal Oxidative Coupling of Aromatic Aldehydes and Isocyanides to α- Ketoamides Supporting information for Zinc Chloride Promoted Formal xidative Coupling of Aromatic Aldehydes and Isocyanides to α- Ketoamides Marinus Bouma, Géraldine Masson* and Jieping Zhu* Institut de Chimie des

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information ~ Experimental Procedures and Spectral/Analytical Data ~ Use of Dimethyl Carbonate as a Solvent Greatly Enhances the Biaryl Coupling of Aryl Iodides and Organoboron

More information

Supporting Materials. Experimental Section. internal standard TMS (0 ppm). The peak patterns are indicated as follows: s, singlet; d,

Supporting Materials. Experimental Section. internal standard TMS (0 ppm). The peak patterns are indicated as follows: s, singlet; d, CuBr-Catalyzed Efficient Alkynylation of sp 3 C-H Bonds Adjacent to a itrogen Atom Zhiping Li and Chao-Jun Li* Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, Quebec H3A

More information

yellow coloured amorphous powder, which on crystallization from hot acetone resulted in pale

yellow coloured amorphous powder, which on crystallization from hot acetone resulted in pale Supporting Information Hexane Extract. Compound I: Elution of column with hexane: dichloromethane (50:50 v/v; 200 ml), gave a pale yellow coloured amorphous powder, which on crystallization from hot acetone

More information

Supporting Information. Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base

Supporting Information. Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base Supporting Information Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base Feng Wang, a Haijun Yang, b Hua Fu, b,c * and Zhichao Pei a * a College

More information

Asymmetric organocatalytic diboration of alkenes

Asymmetric organocatalytic diboration of alkenes Asymmetric organocatalytic diboration of alkenes Amadeu Bonet, a Cristina Solé, Henrik Gulyás,* Elena Fernández* a Dept. Química Física i Inorgànica, University Rovira i Virgili, C/Marcel lí Domingo s/n,

More information

Supporting Information for. Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of. 3,5-Disubstituted Pyridines: Mechanistic Studies

Supporting Information for. Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of. 3,5-Disubstituted Pyridines: Mechanistic Studies Supporting Information for Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of 3,5-Disubstituted Pyridines: Mechanistic Studies Ta-Hsien Chuang* a, Yu-Chi Chen b and Someshwar Pola

More information

Ethyl 2-hydroxy-4-methyl-1-((prop-2-yn-1-yloxy)methyl)cyclohex-3-enecarboxylate (16):

Ethyl 2-hydroxy-4-methyl-1-((prop-2-yn-1-yloxy)methyl)cyclohex-3-enecarboxylate (16): General methods: 1 H NMR and 13 C NMR spectra were recorded in CDCl 3 or CDCl3 and CCl 4 as solvent on 300 MHz or 500 MHz spectrometer at ambient temperature. The coupling constant J is given in Hz. The

More information

Catalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds

Catalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds Catalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds Cui-Feng Yang, Jian-Yong Wang and Shi-Kai Tian* Joint Laboratory of Green

More information

ph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors

ph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors ph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors Jie Li, Chendong Ji, Wantai Yang, Meizhen Yin* State Key Laboratory of Chemical Resource Engineering,

More information

Cu-Catalyzed Direct C6-Arylation of Indoles

Cu-Catalyzed Direct C6-Arylation of Indoles Cu-Catalyzed Direct C6-Arylation of Indoles (Supporting Information) Youqing Yang, Ruirui Li, Yue Zhao, Dongbing Zhao, and Zhuangzhi Shi*, State Key Laboratory of Coordination Chemistry, Collaborative

More information

Electronic Supplementary Information. Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of

Electronic Supplementary Information. Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of Electronic Supplementary Information Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of Allylic Alcohols: An Effective and Enantioselective Approach to α Quaternary β Fluoro

More information

Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF

Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF Supporting information Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF Otome E. Okoromoba, a Gerald B. Hammond, a, * Bo Xu b, * a Department

More information

Thiol-Activated gem-dithiols: A New Class of Controllable. Hydrogen Sulfide (H 2 S) Donors

Thiol-Activated gem-dithiols: A New Class of Controllable. Hydrogen Sulfide (H 2 S) Donors Thiol-Activated gem-dithiols: A New Class of Controllable Hydrogen Sulfide (H 2 S) Donors Yu Zhao, Jianming Kang, Chung-Min Park, Powell E. Bagdon, Bo Peng, and Ming Xian * Department of Chemistry, Washington

More information

Supporting Information. Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as

Supporting Information. Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as Supporting Information Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as CO Source Guanglong Sun,,, Xue Lv,,, Yinan Zhang, Min Lei,*,, and Lihong Hu*, Jiangsu Key Laboratory for Functional

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supporting Information Facile Three-Step Synthesis and Photophysical Properties of [8]-, [9]-,

More information

Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles. Supporting Information

Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles. Supporting Information Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles Vinaykumar Kanchupalli, Desna Joseph and Sreenivas Katukojvala* Department of Chemistry, Indian Institute

More information

Supporting Information. Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition

Supporting Information. Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition Supporting Information Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition Shan Xu, Juyou Lu and Hua Fu* Key Laboratory of Bioorganic Phosphorus Chemistry and

More information

Supporting Information. Recyclable hypervalent-iodine-mediated solid-phase peptide

Supporting Information. Recyclable hypervalent-iodine-mediated solid-phase peptide Supporting Information Recyclable hypervalent-iodine-mediated solid-phase peptide synthesis and cyclic peptide synthesis Dan Liu, Ya-Li Guo, Jin Qu and Chi Zhang* for Address: State Key Laboratory of Elemento-Organic

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Enantioselective Cu-catalyzed 1,4-Addition of Various Grignard Reagents to Cyclohexenone using Taddol-derived Phosphine-Phosphite

More information

Synergistic Cu-amine catalysis for the enantioselective synthesis of chiral cyclohexenones

Synergistic Cu-amine catalysis for the enantioselective synthesis of chiral cyclohexenones Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Synergistic Cu-amine catalysis for the enantioselective synthesis of chiral cyclohexenones Adrien

More information

Ynamides as racemization-free coupling reagents for amide and peptide synthesis

Ynamides as racemization-free coupling reagents for amide and peptide synthesis Ynamides as racemization-free coupling reagents for amide and peptide synthesis Long Hu, Silin Xu, Zhenguang Zhao, Yang Yang, Zhiyuan Peng, Ming Yang, Changliu Wang, Junfeng Zhao* Key Laboratory of Chemical

More information

Supporting Information for. Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the. analysis of Glucose in Whole Blood

Supporting Information for. Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the. analysis of Glucose in Whole Blood Supporting Information for Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the analysis of Glucose in Whole Blood Yueling Liu, Jingwei Zhu, Yanmei Xu, Yu Qin*, Dechen Jiang*

More information

Supporting Information

Supporting Information Supporting Information Synthesis of N-Heteropolycyclic Compounds Including Quinazolinone Skeletons by Using Friedel-Crafts Alkylation Bu Keun Oh, Eun Bi Ko, Jin Wook Han* and Chang Ho Oh* Department of

More information

Supporting Information

Supporting Information Supporting Information Unconventional Passerini Reaction towards α-aminoxyamides Ajay L. Chandgude, Alexander Dömling* Department of Drug Design, University of Groningen, Antonius Deusinglaan 1, 9713 AV

More information

Scheme S1. Synthesis of glycose-amino ligand.

Scheme S1. Synthesis of glycose-amino ligand. Scheme S1. Synthesis of glycose-amino ligand. 5-Chloro-1-pentyl-2,3,4,6-tetra-O-acetyl-ß-D-glucopyranoside S2 To a solution of penta-o-acetyl-ß-d-glucopyranoside S1 (3.0 g, 7.69 mmol) and 5-chloropentan-1-ol

More information

Supplementary Materials Contents

Supplementary Materials Contents Supplementary Materials Contents Supporting information... S1 1. General Information & Materials... S2 2. General Procedure for ptimization of Amidation of Aryl Bromides with Copper/,-Dimethylglycine Catalytic

More information

Supporting Information

Supporting Information J. Am. Chem. Soc. Supporting Information S 1 Enantioselective rganocatalytic Indole Alkylations. Design of a New and Highly Effective Chiral Amine for Iminium Catalysis. Joel F. Austin and David W. C.

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for rganic Chemistry Frontiers. This journal is the Partner rganisations 2016 Supporting Information Fangyi Li, Changgui Zhao, and Jian Wang* Department of Pharmacology

More information

Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis

Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis Greg P. Iacobini, a David W. Porter, b and Michael Shipman* a a Department

More information

The First Au-Nanoparticles Catalyzed Green Synthesis of Propargylamines Via Three-Component Coupling Reaction of Aldehyde, Alkyne And Amine

The First Au-Nanoparticles Catalyzed Green Synthesis of Propargylamines Via Three-Component Coupling Reaction of Aldehyde, Alkyne And Amine Supporting information of The First Au-anoparticles Catalyzed Green Synthesis of Propargylamines Via Three-Component Coupling Reaction of Aldehyde, Alkyne And Amine Mazaahir Kidwai a *, Vikas Bansal a,

More information

# Supplementary Material (ESI) for Chemical Communications # This journal is The Royal Society of Chemistry 2005

# Supplementary Material (ESI) for Chemical Communications # This journal is The Royal Society of Chemistry 2005 Electronic Supplementary Information for: (Z)-Selective cross-dimerization of arylacetylenes with silylacetylenes catalyzed by vinylideneruthenium complexes Hiroyuki Katayama,* Hiroshi Yari, Masaki Tanaka,

More information

PREPARATION OF OPTICALLY ACTIVE 2,2-DISUBSTITUTED 5-HYDROXYCHROMENES BY ENZYMATIC RESOLUTION OF RACEMIC ESTERS

PREPARATION OF OPTICALLY ACTIVE 2,2-DISUBSTITUTED 5-HYDROXYCHROMENES BY ENZYMATIC RESOLUTION OF RACEMIC ESTERS 604 HETEROCYCLES, Vol. 97, No. 1, 2018 HETEROCYCLES, Vol. 97, No. 1, 2018, pp. 604-611. 2018 The Japan Institute of Heterocyclic Chemistry Received, 13th February, 2018, Accepted, 8th May, 2018, Published

More information

Supplemental Material

Supplemental Material Supplemental Material General Methods Unless otherwise indicated, all anhydrous solvents were commercially obtained and stored under nitrogen. Reactions were performed under an atmosphere of dry nitrogen

More information

Electronic Supplementary Information

Electronic Supplementary Information Efficient aerobic oxidative synthesis of 2-aryl quinazolines via benzyl C-H bond amination catalyzed by 4-hydroxy-TEMPO Bing Han,* Chao Wang, Run-Feng Han, Wei Yu,* Xiao-Yong Duan, Ran Fang and Xiu-Long

More information

One-pot Synthesis of 1-Alkyl-1H-indazoles. Supporting Information

One-pot Synthesis of 1-Alkyl-1H-indazoles. Supporting Information One-pot Synthesis of 1-Alkyl-1H-indazoles from 1,1-Dialkylhydrazones via Aryne Annulation ataliya A. Markina, Anton V. Dubrovskiy, and Richard C. Larock* Department of Chemistry, Iowa State University,

More information

Supporting Information. for. Access to pyrrolo-pyridines by gold-catalyzed. hydroarylation of pyrroles tethered to terminal alkynes

Supporting Information. for. Access to pyrrolo-pyridines by gold-catalyzed. hydroarylation of pyrroles tethered to terminal alkynes Supporting Information for Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes Elena Borsini 1, Gianluigi Broggini* 1, Andrea Fasana 1, Chiara Baldassarri

More information

Development of a near-infrared fluorescent probe for monitoring hydrazine in serum and living cells

Development of a near-infrared fluorescent probe for monitoring hydrazine in serum and living cells Supporting Information for Development of a near-infrared fluorescent probe for monitoring hydrazine in serum and living cells Sasa Zhu, Weiying Lin,* Lin Yuan State Key Laboratory of Chemo/Biosensing

More information

Direct ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle

Direct ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle Direct ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle Kun Guo, Xiaolan Chen, Mingyu Guan, and Yingsheng Zhao* Key Laboratory of Organic Synthesis of

More information

Supporting Information

Supporting Information Supporting Information Asymmetric organocatalytic formation of protected and unprotected tetroses under potentially prebiotic conditions. Laurence Burroughs, Paul A. Clarke,* Henrietta Forintos, James

More information

Structure and conserved function of iso-branched sphingoid bases from the nematode Caenorhabditis elegans

Structure and conserved function of iso-branched sphingoid bases from the nematode Caenorhabditis elegans Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 207 Structure and conserved function of iso-branched sphingoid bases from the nematode Caenorhabditis

More information

Supporting Information. Radical fluorination powered expedient synthesis of 3 fluorobicyclo[1.1.1]pentan 1 amine

Supporting Information. Radical fluorination powered expedient synthesis of 3 fluorobicyclo[1.1.1]pentan 1 amine Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information Radical fluorination powered expedient synthesis

More information

Methyltrioxorhenium-Catalyzed Highly Selective Dihydroxylation of 1,2-Allenylic Diphenyl Phosphine Oxides

Methyltrioxorhenium-Catalyzed Highly Selective Dihydroxylation of 1,2-Allenylic Diphenyl Phosphine Oxides Electronic Supplementary Material (ESI) for Chemical Communications. This journal is The Royal Society of Chemistry 2015 Methyltrioxorhenium-Catalyzed Highly Selective Dihydroxylation of 1,2-Allenylic

More information

Supporting Information

Supporting Information Supporting Information Direct Synthesis of Benzimidazoles by Dehydrogenative Coupling of Aromatic Diamines and Alcohols Catalyzed by Cobalt Prosenjit Daw, Yehoshoa Ben-David, and David Milstein* Department

More information

Supporting Information. Nitrodibenzofuran: a One- and Two-Photon Sensitive Protecting Group that is Superior to

Supporting Information. Nitrodibenzofuran: a One- and Two-Photon Sensitive Protecting Group that is Superior to Supporting Information Nitrodibenzofuran: a One- and Two-Photon Sensitive Protecting Group that is Superior to Brominated Hydroxycoumarin for Thiol Caging in Peptides M. Mohsen Mahmoodi, Daniel Abate-Pella,

More information

Supporting Information. Total Synthesis of Grandisine D. Haruaki Kurasaki, Iwao Okamoto, Nobuyoshi Morita, and Osamu Tamura*

Supporting Information. Total Synthesis of Grandisine D. Haruaki Kurasaki, Iwao Okamoto, Nobuyoshi Morita, and Osamu Tamura* Supporting Information Total Synthesis of Grandisine D Haruaki Kurasaki, Iwao Okamoto, Nobuyoshi Morita, and Osamu Tamura* Discovery Research Laboratories, Kyorin Pharmaceutical Co. Ltd. 2399-1, Nogi,

More information

Supporting Information

Supporting Information Supporting Information B(C 6 F 5 ) 3 -catalyzed Regioselective Deuteration of Electronrich Aromatic and Heteroaromatic compounds Wu Li, Ming-Ming Wang, Yuya Hu and Thomas Werner* Leibniz-Institute of Catalysis

More information

Supporting Information. Use of Potassium. -Trifluoroborato Amides in Suzuki-Miyaura. Cross-Coupling Reactions

Supporting Information. Use of Potassium. -Trifluoroborato Amides in Suzuki-Miyaura. Cross-Coupling Reactions Supporting Information Use of Potassium -Trifluoroborato Amides in Suzuki-Miyaura Cross-Coupling Reactions Gary A. Molander* and Ludivine Jean-Gérard Roy and Diana Vagelos Laboratories, Department of Chemistry,

More information

Allenylphosphine oxides as simple scaffolds for. phosphinoylindoles and phosphinoylisocoumarins

Allenylphosphine oxides as simple scaffolds for. phosphinoylindoles and phosphinoylisocoumarins Supporting Information for Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins G. Gangadhararao, Ramesh Kotikalapudi, M. Nagarjuna Reddy and K. C. Kumara Swamy*

More information

Synthesis and Assignment of the Absolute Configuration of an Indenotryptoline Bisindole Alkaloid, BE-54017

Synthesis and Assignment of the Absolute Configuration of an Indenotryptoline Bisindole Alkaloid, BE-54017 Supporting Information Synthesis and Assignment of the Absolute Configuration of an Indenotryptoline Bisindole Alkaloid, BE-54017 Tomoyuki Kimura, Shuhei Kanagaki, Yusuke Matsui, Masaya Imoto, Takumi Watanabe*,,

More information

Supporting Information

Supporting Information Palladium-Catalyzed Cascade Oxidantion/sp 2 C-H Acylation of Azoarenes with Aryl Methanes Feng Xiong, a Cheng Qian, b Dongen Lin, b Wei Zeng b,* and Xiaoxia Lu a,* a Chengdu Institute of Biology,CAS, Chengdu

More information

Novel D-erythro N-Octanoyl Sphingosine Analogs As Chemo- and Endocrine. Resistant Breast Cancer Therapeutics

Novel D-erythro N-Octanoyl Sphingosine Analogs As Chemo- and Endocrine. Resistant Breast Cancer Therapeutics Page 11 of 32 Cancer Chemotherapy and Pharmacology Novel D-erythro N-Octanoyl Sphingosine Analogs As Chemo- and Endocrine Resistant Breast Cancer Therapeutics James W. Antoon, Jiawang Liu, Adharsh P. Ponnapakkam,

More information

Nitro-Grela-type complexes containing iodides. robust and selective catalysts for olefin metathesis

Nitro-Grela-type complexes containing iodides. robust and selective catalysts for olefin metathesis Supporting Information for Nitro-Grela-type complexes containing iodides robust and selective catalysts for olefin metathesis under challenging conditions. Andrzej Tracz, 1,2 Mateusz Matczak, 1 Katarzyna

More information

Base-promoted acetal formation employing aryl salicylates

Base-promoted acetal formation employing aryl salicylates Base-promoted acetal formation employing aryl salicylates Pinmanee Boontheung, Patrick Perlmutter*, and Evaloni Puniani School of Chemistry, Monash University, PO Box 23, Victoria 3800 Australia E-mail:

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information A Novel and Facile Zn-mediated Intramolecular Five-membered Cyclization of β-tetraarylporphyrin Radicals from β-bromotetraarylporphyrins Dong-Mei Shen, Chao Liu, Qing-Yun

More information

Simple copper/tempo catalyzed aerobic dehydrogenation. of benzylic amines and anilines

Simple copper/tempo catalyzed aerobic dehydrogenation. of benzylic amines and anilines Simple copper/tempo catalyzed aerobic dehydrogenation of benzylic amines and anilines Zhenzhong Hu and Francesca M. Kerton,* Department of Chemistry, Memorial University of Newfoundland, St. John s, NL,

More information

Supporting Information. Asymmetric Formation of tert-alkylamines from Serinols by a Dual Function Catalyst

Supporting Information. Asymmetric Formation of tert-alkylamines from Serinols by a Dual Function Catalyst Supporting Information Asymmetric Formation of tert-alkylamines from Serinols by a Dual Function Catalyst Young Suk You, Tae Woo Kim and Sung Ho Kang* Molecular-Level Interface Research Center (MIRC),

More information

Eur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION

Eur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION Eur. J. Org. Chem. 2007 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 ISSN 1434 193X SUPPORTING INFORMATION Title: Effect of Varying the Anionic Component of a Copper(I) Catalyst on Homologation

More information

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 Supporting Information General. NMR spectra for identification of intermediates and final compoundswere recorded

More information

Supporting Information. for. Synthesis of dye/fluorescent functionalized. dendrons based on cyclotriphosphazene

Supporting Information. for. Synthesis of dye/fluorescent functionalized. dendrons based on cyclotriphosphazene Supporting Information for Synthesis of dye/fluorescent functionalized dendrons based on cyclotriphosphazene Aurélien Hameau 1,2, Sabine Fuchs 1,2, Régis Laurent 1,2, Jean-Pierre Majoral* 1,2 and Anne-Marie

More information

On the Utility of S-Mesitylsulfinimines for the Stereoselective Synthesis of Chiral Amines and Aziridines

On the Utility of S-Mesitylsulfinimines for the Stereoselective Synthesis of Chiral Amines and Aziridines n the Utility of S-Mesitylsulfinimines for the Stereoselective Synthesis of Chiral Amines and Aziridines Caroline Roe, a Toni Moragas Solá, a Leonid Sasraku-eequaye, b eather obbs, c Ian Churcher, c David

More information

Supporting Information

Supporting Information Investigation of self-immolative linkers in the design of hydrogen peroxide metalloprotein inhibitors Jody L. Major Jourden, Kevin B. Daniel, and Seth M. Cohen* Department of Chemistry and Biochemistry,

More information

Schwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins

Schwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins Electronic Supplementary Information (ESI) Schwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins A. Ulikowski and B. Furman* Institute of Organic Chemistry, Polish

More information

THE JOURNAL OF ANTIBIOTICS. Polyketomycin, a New Antibiotic from Streptomyces sp. MK277-AF1. II. Structure Determination

THE JOURNAL OF ANTIBIOTICS. Polyketomycin, a New Antibiotic from Streptomyces sp. MK277-AF1. II. Structure Determination THE JOURNAL OF ANTIBIOTICS Polyketomycin, a New Antibiotic from Streptomyces sp. MK277-AF1 II. Structure Determination ISAO MOMOSE, WEI CHEN, HIKARU NAKAMURA, HIROSHI NAGANAWA, HIRONOBU IINUMA and TOMIO

More information

Direct Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source

Direct Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source Direct Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source Xuesong Wu, Yan Zhao, and Haibo Ge* Table of Contents General Information...

More information

An Unusual Glycosylation Product from a Partially Protected Fucosyl Donor. under Silver Triflate activation conditions. Supporting information

An Unusual Glycosylation Product from a Partially Protected Fucosyl Donor. under Silver Triflate activation conditions. Supporting information An Unusual Glycosylation Product from a Partially Protected Fucosyl Donor under Silver Triflate activation conditions Robin Daly a and Eoin M. Scanlan* a e-mail: eoin.scanlan@tcd.ie a Trinity Biomedical

More information

Supporting Information

Supporting Information Supporting Information Enantioselective Phosphine-Catalyzed Allylic Alkylations of mix- Indene with MBH Carbonates Junyou Zhang, Hai-Hong Wu,* and Junliang Zhang* Shanghai Key Laboratory of Green Chemistry

More information

mm C3a. 1 mm C3a Time (s) C5a. C3a. Blank. 10 mm Time (s) Time (s)

mm C3a. 1 mm C3a Time (s) C5a. C3a. Blank. 10 mm Time (s) Time (s) 125 I-C5a (cpm) Fluorescnece Em 520nm a 4000 3000 2000 1000 c 0 5000 4000 3000 2000 Blank C5a C3a 6 0.3 mm C3a 7 9 10 11 12 13 15 16 0.3 mm C5a 0 300 600 900 1200 Time (s) 17 Fluorescnece Em 520nm Fluorescnece

More information

Palladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation

Palladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation 1 Palladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation Zhen-Kang Wen, Yun-He Xu* and Teck-Peng Loh* Division of Chemistry and

More information

Graduate School of Nutritional and Environmental Sciences, University of Shizuoka,

Graduate School of Nutritional and Environmental Sciences, University of Shizuoka, Identification of Indole Alkaloid Structural Units Important for Stimulus Selective TRPM8 Inhibition: SAR Study of Naturally Occurring Iboga Derivatives Yuko Terada,, Mariko Kitajima,, Fuyumi Taguchi,

More information

Supporting Information

Supporting Information Supporting Information Synthesis of Pyrido-fused Quinazolinone Derivatives via Copper-catalyzed Domino Reaction Meilin Liu, Miaomiao Shu, Chaochao Yao, Guodong Yin,* Dunjia Wang, and Jinkun Huang* Hubei

More information

Naoya Takahashi, Keiya Hirota and Yoshitaka Saga* Supplementary material

Naoya Takahashi, Keiya Hirota and Yoshitaka Saga* Supplementary material Supplementary material Facile transformation of the five-membered exocyclic E-ring in 13 2 -demethoxycarbonyl chlorophyll derivatives by molecular oxygen with titanium oxide in the dark Naoya Takahashi,

More information

Improved Carbonylation of Heterocyclic Chlorides and Challenging Aryl Bromides

Improved Carbonylation of Heterocyclic Chlorides and Challenging Aryl Bromides Albaneze-Walker et al S-1 Improved Carbonylation of Heterocyclic Chlorides and Challenging Aryl Bromides Jennifer Albaneze-Walker*, Charles Bazaral, Tanya Leavey, Peter G. Dormer, and Jerry A. Murry Department

More information

NHC-catalyzed cleavage of vicinal diketones and. triketones followed by insertion of enones and

NHC-catalyzed cleavage of vicinal diketones and. triketones followed by insertion of enones and Supporting Information for NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones Ken Takaki*, Makoto Hino, Akira Ohno, Kimihiro Komeyama, Hiroto Yoshida

More information

L-Carnosine-Derived Fmoc-Tripeptides Forming ph- Sensitive and Proteolytically Stable Supramolecular

L-Carnosine-Derived Fmoc-Tripeptides Forming ph- Sensitive and Proteolytically Stable Supramolecular Supporting Information: L-Carnosine-Derived Fmoc-Tripeptides Forming ph- Sensitive and Proteolytically Stable Supramolecular Hydrogels Rita Das Mahapatra, a Joykrishna Dey* a, and Richard G. Weiss b a

More information

Supporting Information. Palladium-catalyzed reductive cleavage of tosylated arene using isopropanol as the mild reducing agent

Supporting Information. Palladium-catalyzed reductive cleavage of tosylated arene using isopropanol as the mild reducing agent Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2014 Supporting Information Supporting Information Palladium-catalyzed reductive cleavage

More information

Supporting Information

Supporting Information Supporting Information Rh(II)-Catalyzed Transannulation of N-Sulfonyl-1,2,3-Triazoles with 2,1-Benzisoxazoles or 1,2-Benzisoxazoles Xiaoqiang Lei, Mohan Gao, Yefeng Tang*,,, E-mail: yefengtang@tsinghua.edu.cn

More information

Supplementary Information. Intramolecular 5-exo, 7-endo-dig Transition Metal-Free Cyclization

Supplementary Information. Intramolecular 5-exo, 7-endo-dig Transition Metal-Free Cyclization Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry Supplementary Information Intramolecular -exo, -endo-dig Transition Metal-Free Cyclization Sequence

More information

Supplementary Figures

Supplementary Figures Supplementary Figures Supplementary Figure 1. 1 H NMR (400 MHz, CDCl3) spectrum of 3a Supplementary Figure 2. 13 C NMR (75 MHz, CDCl3) spectrum of 3a 1 Supplementary Figure 3. 1 H NMR (400 MHz, CDCl3)

More information

SUPPORTING INFORMATION. Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S

SUPPORTING INFORMATION. Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S 1 SUPPORTING INFORMATION Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S Bond formation by Chan-Lam Cross-Coupling Reaction SATYA KARUNA PULAKHANDAM a, NARESH KUMAR KATARI

More information