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1 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 and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, (P. R. China), Table of Contents 1. General Information Typical Procedure for Synthesis of (S, R S )-P General Procedure for the Chiral Phosphine Catalyzed Allylic Alkylations of mix-indene with MBH Carbonates Proposed Mechanism for Allylic Alkylation Reaction Optimization Conditions General Data and HPLC Spectra for 3 and 5c Experimental Procedure for the Transformations of 3g Typical Procedure for Synthesis the Starting Materials of General Data for Starting Material of 1 and X-ray Crystal Ttructure for References H, 13 C, 19 F, 31 P Spectra of Compounds

2 1. General Information Unless otherwise noted, all reactions were carried out under a nitrogen atmosphere; materials obtained fromcommercial suppliers were used directly without further purification. The [α] D was recorded using PolAAr 3005 High Accuracy Polarimeter. 1 H NMR spectra and 13 C NMR spectra were recorded on a Bruker 400 (or 500) MHz spectrometer in chloroform-d3. 19 F NMR were recorded on a Bruker 400 MHz spectrometer in chloroform-d3. Chemical shifts (in ppm) were referenced to tetramethylsilane (δ = 0 ppm) in CDCl3 as an internal standard. 13 C NMR spectra were obtained by using the same NMR spectrometers and were calibrated with CDCl3 (δ = ppm). The data is being reported as (s = singlet, d = doublet, dd = doublet of doublet, t = triplet, m = multiplet or unresolved, br = broad signal, coupling constant(s) in Hz, integration). Noteworthy, splitting signals of 13 C nucleus was difficult to distinguish and these 13 C NMR signals were reported as singlet entirely. Trichloromethane (CHCl3), dichloromethane, dichloroethane and ethyl acetate were freshly distilled from CaH2; tetrahydrofuran (THF), toluene and ether were dried with sodium benzophenone and distilled before use; Ph2PCH3 was purchased from AcrosCompany. Reactions were monitored by thin layer chromatography (TLC) using silicycle pre-coated silica gel plates. Flash column chromatography was performed on silica gel 60 (particle size mesh ASTM, purchased from Yantai, China) and eluted with petroleum ether/ethyl acetate. 2

3 2. Typical Procedure for Synthesis of (S, R S )-P9 The chiral sulfinyl imine was prepared according to the literature [1] and the chiral sulfinamide phosphine catalyst (S, RS)-P9 was prepared according to the previous work for our group [5b]. The compound S9 was reported in literature [1]. The experimental data was completely matched with the reported value. The date for (S, RS)-P8: white solid. 1 H NMR (300 MHz, CDCl3) δ (m, 4H), (m, 6H), (m, 2H), 2.21 (m, 3H), 1.16 (s, 9H), 0.96 (d, J = 6.9 Hz, 3H), 0.89 (d, J = 6.9 Hz, 3H); 31 P NMR (122 MHz, CDCl3) δ The date for (S, RS)-P9: white solid. [±]D 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 6H), (m, 1H), 3.15 (d, J = 7.2 Hz, 1H), 2.45 (dd, J = 14.0, 6.8 Hz, 1H), 2.22 (dd, J = 14.0, 6.8 Hz, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.14 (s, 9H); 13 C NMR (100 MHz, CDCl3) δ (d, J = 13.4 Hz), (d, J = 12.1 Hz), , , , , , (d, J = 1.5 Hz), , 55.82, (d, J = 16.8 Hz), (d, J = 14.5 Hz), (d, J = 8.1 Hz), P NMR (162 MHz, CDCl3): ; HRMS (EI) calcd for C19H26NOPS, m/z = (M + ); found, m/z =

4 3. General Procedure for the chiral phosphine Catalyzed allylic alkylations of mix-indene with MBH carbonates All 3-(trifluoromethyl)-1H-indene derivatives 1 was synthesized according to the method reported in previous article with slight modifications [2]. 4 was synthesized according to the literature procedure [3]. All MBH carbonates 2 were synthesized according to the literature procedure [4]. All chiral sulfinamide phosphine catalysts were synthesized according to our previous work [5]. All the reactions use the Ph2PCH3 as the racemic catalyst. All reactions were carried out under a nitrogen atmosphere, a stirred solution of 1 or 4 (0.1 mmol) and (S, RS)-P8 (0.01 mmol) in dry toluene (2 ml) at ambient temperature was added MBH carbonate 2 (0.15 mmol) slowly. The mixture was stirred for another 8-12 h at same temperature. After consumption of 1 or 4 (monitored by TLC), the solvent was removed in vacuo and the residue was purified directly by column chromatography on silica gel using petroleum ether/ethyl acetate or hexane/dcm as the eluent to afford the desired product 3 or 5. The enantiomeric excesses of the products were determined by chiral stationary phase HPLC using a Chiralpak AD-H, ODH, OJ-H or both of them. 4

5 4. Optimization of reaction conditions Table S1: Optimization of conditions for simple MBH carbonate 2a a. entry 1 cat.* solvent 3a yield[%](mg) b 3a ee[%] c 1 1a (S, RS)-P1 toluene 88(31.5) a (S, RS)-P2 toluene 85(30.4) a (S, RS)-P3 toluene 87(31.0) a (S, RS)-P4 toluene 43(15.3) a (S, RS)-P5 toluene 85(30.4) a (S, RS)-P6 toluene 85(30.5) 89 7 d 1a (S, RS)-P6 toluene 68(24.3) 95 8 e 1a (S, RS)-P6 toluene 61(22.0) a (S, RS)-P7 toluene 82(29.2) a (S, RS)-P8 toluene 85(32.9) a (S, RS)-P9 toluene 88(31.6) a (S)-P10 toluene 78(28.0) a (S, RS)-P11 toluene 0(0) a (S, RS)-P8 DCM 87(31.0) a (S, RS)-P8 DCE 86(30.9) a (S, RS)-P8 THF 71(25.3) a (S, RS)-P8 Et2O 53(19.1) a (S, RS)-P8 CH3CN 46(16.3) a (S, RS)-P8 1,4-dioxane 0(0) 0 20 f 1a (S, RS)-P8 toluene 71(25.4) g 1a (S, RS)-P8 toluene 47(16.9) h 1a (S, RS)-P8 toluene 35(12.7) a' (S, RS)-P8 toluene 84(30.1) i 1a+1a' (S, RS)-P8 toluene 87(31.0) 95 a Unless otherwise specified, all reactions were carried out with 1 (0.1 mmol), 2a (0.15 mmol), chiral phosphine catalyst (10 mol %) in solvent (2 ml), 20, 3a:3a' > 49:1. b Isolated yield. c Determined by HPLC analysis using a chiral stationary. d 0 instead. e -25 instead. f 7.5 mol % cat.* used. g 5 mol % cat.* used. h 2.5 mol % cat.* used. i 1a:1a' = 1:1. 5

6 Table S2: Optimization of conditions for MBH carbonate 2f a. entry cat. solvent base T 5a yield[mg] b 5a' yield[mg] b 1 Ph3P toluene - c 20 NR d NR 2 Ph2PMe toluene - 20 NR NR 3 e Ph2PMe toluene KO t Bu 20 NR NR 4 (S, RS)-P1 toluene - 20 NR NR 5 (S, RS)-P2 toluene - 20 NR NR 6 (S, RS)-P3 toluene - 20 NR NR 7 (S, RS)-P6 toluene - 20 NR NR 8 (S, RS)-P8 toluene - 20 NR NR 9 (S, RS)-P9 toluene - 20 NR NR 10 (S, RS)-P2 toluene - 50 NR NR 11 (S, RS)-P3 toluene - 50 NR NR 12 (S, RS)-P6 toluene - 50 NR NR 13 (S, RS)-P9 toluene - 50 NR NR 14 (S, RS)-P8 THF - 20 NR NR 15 (S, RS)-P8 DCM - 20 NR NR a Unless otherwise specified, all reactions were carried out with 1a (0.1 mmol), 2f (0.15 mmol), phosphine catalyst (10 mol %) in solvent (2 ml), T. b Isolated yield. c - = No base. d NR = No reaction. 6

7 Table S3: Optimization of conditions for MBH carbonate 2g a. entry cat. solvent T 5b yield[mg] b 5b' yield[mg] b 1 Ph3P toluene 20 NR NR 2 Ph2PCH3 toluene 20 NR NR 3 (S, RS)-P1 toluene 20 NR NR 4 (S, RS)-P2 toluene 20 NR NR 6 (S, RS)-P6 toluene 20 NR NR 7 (S, RS)-P8 toluene 20 NR NR 8 (S, RS)-P9 toluene 20 NR NR a Unless otherwise specified, all reactions were carried out with 1a (0.1 mmol), 2f (0.15 mmol), phosphine catalyst (10 mol %) in solvent (2 ml), T. b Isolated yield. c NR = No reaction. 5. Proposed Mechanism for Allylic Alkylation Reaction Scheme S1. Proposed mechanism and chirality induction model 7

8 A plausible reaction mechanism and catalytic mode for this chiral phosphinecatalyzed AAA reaction is outlined in Scheme S1. Firstly, nucleophilic attack of the P8 to the MBH carbonate 2 yields a chiral quaternary phosphonium salt B and the in-situ generated tert-butoxide deprotonates indene 1a or 1a' forming an allylic carboanion A, which undergoes an SN2' reaction with phosphoniun salt B to de-liver the corresponding enantioenriched γ-allylation product 3 with the C1-quaternary center to regenerate the catalyst. 8

9 6. General Data and HPLC Spectra for 3 and 5a 3a (R)-methyl-2-((3-phenyl-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 20, 12 h, 3a (30.4 mg, 85%) was obtained as a colorless oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 7.2 Hz, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 2H), 6.30 (s, 1H), 5.79 (d, J = 1.2 Hz, 1H), 5.05 (s, 1H), 3.60 (s, 3H), 3.49 (d, J = 12.8 Hz, 1H), 3.11 (d, J = 12.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , (d, JC, F = 1.5 Hz), , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.1 Hz), 51.84, (d, JC, F = 2.0 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 97%, determined by HPLC (Chiralpak OD-H, hexane/i- PrOH = 97.5/2.5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 8.88 min, second peak: tr = 9.64 min; HRMS (ESI) m/z calcd. for C21H17F3NaO2 [M+Na] + = , found =

10 3b (R)-methyl-2-((5-methyl-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 19, 12 h, 3b (32.9 mg, 88%) was obtained as a colorless oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 2H), (m, 1H), 7.25 (s, 1H), 7.13 (d, J = 8.0 Hz, 1H), 6.27 (s, 1H), 5.81 (d, J = 1.2 Hz, 1H), 5.07 (s, 1H), 3.61 (s, 3H), 3.47 (d, J = 13.2 Hz, 1H), 3.08 (d, J = 12.8 Hz, 1H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.0 Hz), 51.81, (d, JC, F = 2.1 Hz), 21.60; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H19F3NaO2 [M+Na] + = , found =

11 3c (R)-methyl-2-((5-methoxy-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 22, 9 h, 3c (32.1 mg, 83%) was obtained as a colorless oil (PE:EA = 10:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.50 (d, J = 7.5 Hz, 2H), 7.43 (t, J = 7.5 Hz, 2H), 7.39 (d, J = 7.5 Hz, 1H), 7.35 (d, J = 8.0 Hz, 1H), 7.16 (s, 1H), 6.89 (dd, J = 8.0, 1.0 Hz, 1H), 6.17 (s, 1H), 5.82 (s, 1H), 5.11 (s, 1H), 3.87 (s, 3H), 3.61 (s, 3H), 3.46 (d, J = 13.0 Hz, 1H), 3.07 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.0 Hz), 55.59, 51.80, (d, JC, F = 1.8 Hz); 19 F NMR (282 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H19F3NaO3 [M+Na] + = , found =

12 3d (R)-methyl-2-((3-phenyl-1,5-bis(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 23, 11 h, 3d (40.2 mg, 94%) was obtained as a light yellow oil (Hexane:EA = 25:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 8.0 Hz, 1H), 7.66 (s, 1H), 7.60 (d, J = 7.8 Hz, 1H), (m, 5H), 6.41 (s, 1H), 5.84 (d, J = 1.0 Hz, 1H), 5.10 (s, 1H), 3.58 (s, 3H), 3.50 (d, J = 13.0 Hz, 1H), 3.16 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , (q, JC, F = 32.0 Hz), , , , , (q, JC, F = Hz), , , (q, JC, F = Hz), (q, JC, F = 3.9 Hz), (q, JC, F = 3.8 Hz), (q, JC, F = 26.4 Hz), 51.91, (d, JC, F = 1.6 Hz); 19 F NMR (282 MHz, CDCl3) δ , ; Enantiomeric excess: 97%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H16F6NaO2 [M+Na] + = , found =

13 3e (R)-methyl-2-((5-fluoro-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 18, 8 h, 3e (29.8 mg, 79%) was obtained as a colorless oil (PE:Et2O = 40:1 as an eluent) in 79% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.52 (dd, J = 8.5, 5.0 Hz, 1H), (m, 5H), 7.13 (dd, J = 9.0, 2.5 Hz, 1H), 7.00 (m, 1H), 6.37 (s, 1H), 5.84 (d, J = 1.0 Hz, 1H), 5.10 (d, J = 1.0 Hz, 1H), 3.60 (s, 3H), 3.46 (d, J = 13.0 Hz, 1H), 3.11 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , (d, JC, F = 2.9 Hz), (d, JC, F = 8.9 Hz), (d, JC, F = 1.1 Hz), , , (d, JC, F = 1.38 Hz), , , , (q, JC, F = Hz), (d, JC, F = 9.3 Hz), (d, JC, F = 23.0 Hz), (d, JC, F = 24.1 Hz), (q, JC, F = 26.4 Hz), 51.88, (d, JC, F = 2.4 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 7.48 min, second peak: tr = 8.11 min; HRMS (ESI) m/z calcd. for C21H16F4NaO2 [M+Na] + = , found =

14 3f (R)-methyl-2-((5-chloro-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 18, 8 h, 3f (35.4 mg, 90%) was obtained as a colorless oil (PE:Et2O = 40:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.50 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 4.5 Hz, 4H), (m, 2H), 7.29 (dd, J = 8.0, 2.0 Hz, 1H), 6.34 (s, 1H), 5.85 (d, J = 1.0 Hz, 1H), 5.11 (d, J = 0.5 Hz, 1H), 3.60 (s, 3H), 3.47 (d, J = 13.0 Hz, 1H), 3.1 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , (d, JC, F = 1.4 Hz), , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.4 Hz), 51.90, (d, JC, F = 2.0 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 7.41 min, second peak: tr = 7.97 min; HRMS (ESI) m/z calcd. for C21H17ClF3O2 [M+H] + = , found =

15 3g (R)-methyl-2-((5-bromo-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 18, 8 h, 3g (38.4 mg, 88%) was obtained as a sticky oil (PE:Et2O = 40:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.56 (t, J = 1.5 Hz, 1H), (m, 6H), (m, 1H), 6.33 (s, 1H), 5.85 (d, J = 1.0 Hz, 1H), 5.11 (d, J = 1.0 Hz, 1H), 3.60 (s, 3H), 3.47 (d, J = 13.0 Hz, 1H), 3.10 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.3 Hz), 51.90, (d, JC, F = 1.9 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 7.45 min, second peak: tr = 8.03 min; HRMS (ESI) m/z calcd. for C21H16BrF3NaO2 [M+Na] + = , found =

16 3h (R)-methyl-2-((5-iodo-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 18, 8 h, 3h (44.3 mg, 92%) was obtained as a colorless oil (PE:Et2O = 40:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.75 (d, J = 1.4 Hz, 1H), 7.66 (dd, J = 8.0, 1.5 Hz, 1H), (m, 4H), (m, 1H), 7.33 (d, J = 7.5 Hz, 1H), 6.28 (s, 1H), 5.85 (d, J = 1.0 Hz, 1H), 5.11 (s, 1H), 3.60 (s, 3H), 3.47 (d, J = 13.0 Hz, 1H), 3.09 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , , (q, JC, F = Hz), , 94.57, (q, JC, F = 26.3 Hz), 51.90, (d, JC, F = 1.8 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 97%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 7.55 min, second peak: tr = 8.19 min; HRMS (ESI) m/z calcd. for C21H17F3IO2 [M+H] + = , found =

17 3i (R)-methyl-2-((7-methyl-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 20, 10 h, 3i (28.5 mg, 77%) was obtained as a colorless oil (Hexane:Et2O = 40:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 2H), (m, 1H), 6.22 (s, 1H), 5.82 (d, J = 0.4 Hz, 1H), 5.08 (s, 1H), 3.57 (s, 3H), 3.45 (d, J = 13.2 Hz, 1H), 3.37 (d, J = 13.6 Hz, 1H), 2.58 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , (d, JC, F = 2.1 Hz), , , , , , , (q, JC, F = Hz), , (q, JC, F = 26.2 Hz), (d, JC, F = 5.1 Hz), 29.52, 19.92; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H19F3NaO2 [M+Na] + = , found =

18 3j (R)-methyl-2-((5,7-dimethyl-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, (S, RS)-P8 (0.015 mmol), 24, 10 h, 3j (36.2 mg, 94%) was obtained as a colorless oil (Hexane:DCM = 5:1 to 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 3H), 6.86 (s, 1H), 5.97 (s, 1H), 5.88 (d, J = 0.8 Hz, 1H), 5.05 (s, 1H), 3.62 (s, 3H), 3.43 (d, J = 12.8 Hz, 1H), 3.03 (d, J = 12.8 Hz, 1H), 2.37 (s, 3H), 1.85 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , (q, JC, F = Hz), , (q, JC, F = 25.8 Hz), 51.80, (d, JC, F = 2.1 Hz), 21.31, 19.77; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 90%, determined by HPLC (Chiralpak OJ-H+OJ-H, hexane/i-proh = 97:3; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C23H22F3O2 [M+H] + = , found = ; 18

19 3k (R)-methyl-2-((7-phenyl-5-(trifluoromethyl)-5H-indeno[5,6-d][1,3]dioxol-5- yl)methyl)acrylate Following general procedure, 20, 8 h, 3k (34.2 mg, 85%) was obtained as a colorless oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 7.07 (s, 1H), 6.90 (s, 1H), 6.18 (s, 1H), 6.01 (dd, J = 8.0, 1.2 Hz, 2H), 5.85 (d, J = 0.8 Hz, 1H), 5.13 (s, 1H), 3.62 (s, 3H), 3.45 (d, J = 12.8 Hz, 1H), 3.02 (d, J = 13.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , (d, JC, F = 1.4 Hz), , , , (q, JC, F = Hz), , , , (q, JC, F = 26.1 Hz), (d, JC, F = 2.0 Hz), (d, JC, F = 2.1 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H18F3O4 [M+H] + = , found = ; 19

20 3l (R)-methyl-2-((5,6-dimethoxy-3-phenyl-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 20, 12 h, 3l (34.1 mg, 82%) was obtained as a colorless oil (Hexane:Et2O = 15:1 to 5:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (300 MHz, CDCl3) δ (m, 5H), 7.12 (s, 1H), 6.95 (s, 1H), 6.18 (s, 1H), 5.80 (d, J = 1.5 Hz, 1H), 5.10 (s, 1H), 3.96 (s, 3H), 3.86 (s, 3H), 3.59 (s, 3H), 3.41 (d, J = 12.9 Hz, 1H), 3.09 (d, J = 12.9 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , (q, JC, F = Hz), , , (q, JC, F = 26.0 Hz), (d, JC, F = 2.6 Hz), (d, JC, F = 2.5 Hz), (d, JC, F = 1.8 Hz)), (d, JC, F = 1.8 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 91%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C23H21F3NaO4 [M+Na] + = , found =

21 3m (R)-methyl-2-((3-phenyl-1-(trifluoromethyl)-1H-cyclopenta[a]naphthalen-1- yl)methyl)acrylate Following general procedure, 20, 12 h, 3m (33.6 mg, 82%) was obtained as a colorless oil (PE:Et2O = 20:1 as an eluent) in 82% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 8.33 (d, J = 9.0 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), (m, 2H), (m, 5H), (m, 1H), 6.46 (s, 1H), 5.62 (d, J = 1.0 Hz, 1H), 4.70 (d, J = 1.0 Hz, 1H), 3.77 (d, J = 13.0 Hz, 1H), 3.50 (s, 3H), 3.49 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , (d, JC, F = 2.4 Hz), , , , , , , , , (q, JC, F = Hz), , (q, JC, F = 4.9 Hz), , (q, JC, F = 26.4 Hz), 51.74, (d, JC, F = 0.9 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 97%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C25H19F3NaO2 [M+Na] + = , found =

22 3n (R)-Methyl-2-((1-phenyl-3-(trifluoromethyl)-3H-cyclopenta[a]naphthalen-3- yl)methyl)acrylate Following general procedure, 17, 10 h, 3n (31.2 mg, 76%) was obtained as a sticky oil (Hexane:EA = 40:1 to 25:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.4 Hz, 1H), 7.84 (d, J = 8.4 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), (m, 6H), (m, 1H), 6.25 (s, 1H), 5.78 (d, J = 0.8 Hz, 1H), 5.00 (s, 1H), 3.58 (d, J = 12.4 Hz, 1H), 3.57 (s, 3H), 3.21 (d, J = 12.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , (d, JC, F = 0.7 Hz), , , , , , , (q, JC, F = Hz), , , , , (q, JC, F = 26.1 Hz), (d, JC, F = 2.5 Hz), (d, JC, F = 1.1 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 98%, determined by HPLC (Chiralpak ID+ID, hexane/i- PrOH = 95:5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (EI) calcd for C25H19O2F3, m/z = (M + ); found, m/z = o 22

23 (R)-methyl-2-((3-(p-tolyl)-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 24, 12 h, 3o (32.7 mg, 88%) was obtained as a colorless oil (Hexane:DCM = 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 7.2 Hz, 1H), 7.44 (d, J = 7.6 Hz, 1H), 7.39 (d, J = 8.0 Hz, 2H), 7.35 (m, 1H), (m, 1H), 7.24 (d, J = 8.0 Hz, 2H), 6.24 (s, 1H), 5.78 (d, J = 0.8 Hz, 1H), 5.04 (s, 1H), 3.59 (s, 3H), 3.46 (d, J = 12.8 Hz, 1H), 3.09 (d, J = 12.8 Hz, 1H), 2.40 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.1 Hz), (d, JC, F = 2.0 Hz), (d, JC, F = 2.0 Hz), (d, JC, F = 2.0 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H20F3O2 [M+H] + = , found = ; 3p 23

24 (R)-methyl-2-((3-(4-chlorophenyl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 17, 10 h, 3p (35.2 mg, 90%) was obtained as a colorless oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.2 Hz, 1H), (m, 7H), 6.30 (s, 1H), 5.80 (d, J = 0.4 Hz, 1H), 5.05 (s, 1H), 3.59 (s, 3H), 3.49 (d, J = 12.8 Hz, 1H), 3.10 (d, J = 12.8 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.3 Hz), 51.81, 32.64; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 95%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 7.90 min, second peak: tr = 8.65 min; HRMS (ESI) m/z calcd. for C21H17ClF3O2 [M+H] + = , found = q 24

25 (R)-methyl-2-((3-(4-bromophenyl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 19, 11 h, 3q (40.4 mg, 93%) was obtained as a colorless oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 5H), 6.30 (s, 1H), 5.79 (d, J = 0.8 Hz, 1H), 5.04 (s, 1H), 3.59 (s, 3H), 3.49 (d, J = 12.8 Hz, 1H), 3.10 (d, J = 13.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , (q, JC, F = Hz), , , , , (q, JC, F = 26.2 Hz), 51.85, (d, JC, F = 1.0 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 8.04 min, second peak: tr = 8.74 min; HRMS (ESI) m/z calcd. for C21H16BrF3NaO2 [M+Na] + = , found = ; 3r 25

26 (R)-methyl-2-((3-(4-cyanophenyl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 23, 11 h, 3r (37.2 mg, 97%) was obtained as a yellow oil (Hexane:EA = 12:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 8.4 Hz, 2H), (m, 3H), (m, 3H), 6.39 (s, 1H), 5.81 (s, 1H), 5.05 (s, 1H), 3.58 (s, 3H), 3.50 (d, J = 12.8 Hz, 1H), 3.10 (d, J = 12.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , (d, JC, F = 1.6 Hz), , , , , (q, JC, F = Hz), , , , , (q, JC, F = 26.2 Hz), 51.87, (d, JC, F = 2.0 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 95%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C22H16F3NNaO2 [M+Na] + = , found = s 26

27 (R)-methyl-2-((3-(3-bromophenyl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 24, 9 h, 3s (36.2 mg, 83%) was obtained as a colorless oil (Hexane:DCM = 8:1 to 5:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.61 (t, J = 2.0 Hz, 1H), 7.59 (d, J = 7.5 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), 6.31 (s, 1H), 5.79 (d, J = 1.0 Hz, 1H), 5.03 (d, J = 0.5 Hz, 1H), 3.62 (s, 3H), 3.50 (d, J = 13.0 Hz, 1H), 3.09 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , (d, JC, F = 1.4 Hz), , , , , (q, JC, F = Hz), , , , , , (q, JC, F = 26.3 Hz), 51.91, (d, JC, F = 2.1 Hz); 19 F NMR (282 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak OD-3+OD-H, hexane/i-proh = 95:5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C21H16BrF3NaO2 [M+Na] + = , found = t 27

28 (R)-methyl-2-((3-(2-bromophenyl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 24, 10 h, 3t (42.8 mg, 98%) was obtained as a colorless oil (Hexane:DCM = 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.66 (dd, J = 8.0, 1.0 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), 6.26 (s, 1H), 5.90 (d, J = 1.0 Hz, 1H), 5.13 (s, 1H), 3.62 (s, 3H), 3.48 (d, J = 13.0 Hz, 1H), 3.15 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , , (q, JC, F = Hz), , , , , (q, JC, F = 26.1 Hz), 51.85, (d, JC, F = 2.0 Hz); 19 F NMR (282 MHz, CDCl3) δ ; Enantiomeric excess: 95%, determined by HPLC (Chiralpak OD-3+OD-H, hexane/i-proh = 95:5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C21H16BrF3NaO2 [M+Na] + = , found = u 28

29 (R)-methyl-2-((3-([1,1'-biphenyl]-4-yl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 20, 12 h, 3u (36.4 mg, 84%) was obtained as a colorless oil (PE:Et2O = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.68 (d, J = 8.0 Hz, 2H), (m, 2H), (m, 3H), (m, 3H), (m, 2H), (t, J = 7.5 Hz, 1H), 6.35 (s, 1H), 5.82 (s, 1H), 5.07 (s, 1H), 3.62 (s, 3H), 3.51 (d, J = 13.0 Hz, 1H), 3.13 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.0 Hz), 51.85, (d, JC, F = 1.8 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 95%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C27H21F3NaO2 [M+Na] + = , found = v 29

30 (R)-methyl-2-((3-(naphthalen-2-yl)-1-(trifluoromethyl)-1H-inden-1- yl)methyl)acrylate Following general procedure, 23, 11 h, 3v (40.0 mg, 98%) was obtained as a colorless oil (Hexane:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 8.01 (s, 1H), (m, 3H), (m, 2H), (m, 3 H), (m, 1H), (m, 1H), 6.42 (s, 1H), 5.84 (d, J = 1.0 Hz, 1H), 5.09 (s, 1H), 3.61 (s, 3H), 3.54 (d, J = 13.0 Hz, 1H), 3.15 (d, J = 13.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , (d, JC, F = 1.25 Hz), , , , , , (q, JC, F = Hz), , , , , , , , (q, JC, F = 26.0 Hz), 51.84, (d, JC, F = 1.9 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 93%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 8.24 min, second peak: tr = 9.09 min; HRMS (ESI) m/z calcd. for C25H19F3NaO2 [M+Na] + = , found = ; 3w 30

31 (R)-ethyl-2-((3-phenyl-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 20, 10 h, 3w (32.5 mg, 87%) was obtained as a colorless oil (PE:DCM = 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.2 Hz, 1H), (m, 2H), (m, 6H), 6.30 (s, 1H), 5.80 (s, 1H), 5.03 (s, 1H), (m, 2H), 3.49 (d, J = 12.8 Hz, 1H), 3.10 (d, J = 12.8 Hz, 1H), 1.15 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , (q, JC, F = Hz), , , , 60.77, (q, JC, F = 26.0 Hz), (q, JC, F = 2.1 Hz), 14.02; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak OD-H, hexane/i- PrOH = 97.5/2.5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = 8.57 min, second peak: tr = 9.35 min; HRMS (ESI) m/z calcd. for C22H19F3NaO2 [M+Na] + = , found = ; 3x 31

32 (R)-isopropyl-2-((3-phenyl-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 20, 10 h, 3x (33.6 mg, 87%) was obtained as a colorless oil (PE:DCM = 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 7.5 Hz, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), 6.31 (s, 1H), 5.79 (d, J = 1.5 Hz, 1H), 5.00 (s, 1H), (m, 1H), 3.49 (d, J = 13.0 Hz, 1H), 3.09 (d, J = 13.0 Hz, 1H), 1.12 (d, J = 6.5 Hz, 3H), 1.09 (d, J = 6.5 Hz, 3H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , (d, JC, F = 1.4 Hz), , , , , , (q, JC, F = Hz), , , , 68.25, (q, JC, F = 26.0 Hz), (d, JC, F = 2.0 Hz), 21.64, 21.54; 19 F NMR (282 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-3+AD-H, hexane/i-proh = 99/1; flow rate 0.3 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (EI) calcd for C23H21O2F3, m/z = (M + ); found, m/z = y 32

33 (R)-tert-butyl-2-((3-phenyl-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 20, 11 h, 3y (34.3 mg, 86%) was obtained as a colorless oil (PE:DCM = 4:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 7.2 Hz, 1H), (m, 2H), 7.45 (dd, J = 14.4, 7.2 Hz, 3H), (m, 1H), (m, 1H), (m, 1H), 6.31 (s, 1H), 5.74 (s, 1H), 4.94 (s, 1H), 3.47 (d, J = 12.8 Hz, 1H), 3.03 (d, J = 13.2 Hz, 1H), 1.31 (s, 9H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , (d, JC, F = 1.5 Hz), , , , , , (q, JC, F = Hz), , , , 80.63, (q, JC, F = 25.9 Hz), (d, JC, F = 2.0 Hz), 27.76; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 95%, determined by HPLC (Chiralpak OD-3+OD-H, hexane/i-proh = 200/1; flow rate 0.3 ml/min; 25 C; 254 nm), first peak: tr = 29.01min, second peak: tr = min; HRMS (ESI) m/z calcd. for C24H23F3NaO2[M+Na] + = , found = z 33

34 (R)-benzyl-2-((3-phenyl-1-(trifluoromethyl)-1H-inden-1-yl)methyl)acrylate Following general procedure, 20, 11 h, 3z (38.8 mg, 89%) was obtained as a light yellow oil (PE:EA = 20:1 as an eluent); [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.2 Hz, 1H), (m, 6H), (m, 1H), (m, 3H), (m, 3H), 6.26 (s, 1H), 5.84 (s, 1H), (m, 3H), 3.51 (d, J = 13.2 Hz, 1H), 3.11 (d, J = 13.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , , , (q, JC, F = Hz), , , , 66.57, (q, JC, F = 26.1 Hz), 32.40; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 94%, determined by HPLC (Chiralpak OD-H, hexane/i- PrOH = 97.5/2.5; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C27H21F3NaO2 [M+Na] + = , found = ; 5c 34

35 (R)-methyl-1-(2-(methoxycarbonyl)allyl)-3-(4-methoxyphenyl)-1H-indene-1- carboxylate Following general procedure, 24, 9 h, 5c (36.8 mg, 97%) was obtained as a colorless oil (PE:EA = 10:1 as an eluent) in 97% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.2 Hz, 1H), 7.48 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 7.2 Hz, 1H), (m, 2H), 6.97 (d, J = 8.8 Hz, 2H), 6.40 (s, 1H), 5.92 (d, J = 0.8 Hz, 1H), 5.22 (s, 1H), 3.85 (s, 3H), 3.67 (s, 3H), 3.64 (s, 3H), 3.46 (d, J = 13.2 Hz, 1H), 3.02 (d, J = 13.6 Hz, 1H); 13 C NMR (125 MHz, CDCl3) δ , , , , , , , , , , , , , , , , 61.81, 55.30, 52.46, 51.80, 37.57; Enantiomeric excess: 90%, determined by HPLC (Chiralpak AD-H, hexane/i- PrOH = 90:10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C23H23O5 [M+H] + = , found = ; 35

36 7. Experimental procedure for the transformations of 3g a) Typical procedure for the hydrolysis of ester A stirred solution of 3g (87.4 mg, 0.2 mmol) in MeCN/H2O (1:1, v/v, 4 ml) was added 1N NaOH (0.5 ml). The mixture was stirred at 60 for 2 h. After completion of the reaction, the reaction mixture was directly applied to a silica gel chromatography column to afford the desired product 6 (78.6 mg, 93%) without loss of enantiopurity. Data and HPLC Spectra for 6: The product was obtained as a white spume solid in 93% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 9.70 (brs, 1H), 7.55 (s, 1H), (m, 7H), 6.32 (s, 1H), 6.04 (s, 1H), 5.23 (s, 1H), 3.45 (d, J = 13.2 Hz, 1H), 3.09 (d, J = 13.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.3 Hz), (d, JC, F = 1.1 Hz); 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H+AD-H, hexane/i-proh = 85/15; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (EI) calcd for C20H14F3O2Br, m/z = (M + ); found, m/z =

37 b) Typical procedure for the reduction of ester To a flame-dried Schlenk tube were added 3g (87.4 mg, 0.2 mmol) and dry DCM (2 ml) was added diisobutyl aluminium hydride (0.53 ml, 4 equiv, 1.5 M in toluene) slowly at -78. The reaction mixture was stirred -78 for 1 h. Then the reaction mixture was quenched with MeOH slowly at -78. Solvent was removed under reduced pressure, and the residue was dissolved in ethyl acetate. A saturated aqueous solution of seignette salt was added until the solution was clean. The aqueous phase was extracted with ethyl acetate. The organic extracts were combined and dried over Na2SO4. Removal of the solvent under reduced pressure left a residue which was purified by column chromatography on silica gel (petroleum ether / ethyl acetate = 7:1) to afford 7 (64.4 mg, 79%) without loss of enantiopurity. Data and HPLC Spectra for 7: The product was obtained as a colorless oil in 79% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), (m, 7H), 6.37 (s, 1H), 4.97 (d, J = 1.2 Hz, 1H), 4.71 (s, 1H), 3.64 (t, J = 14.8 Hz, 2H), 3.07 (d, J = 13.6 Hz, 1H), 3.00 (d, J = 13.6 Hz, 1H), 1.28 (d, J = 10.0 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , (q, JC, F = Hz), , , , , 65.99, (q, JC, F = 25.8 Hz), 33.76; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak AD-H+AD-3, hexane/i-proh = 90/10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (EI) calcd for C20H16F3OBr, m/z = (M + ); found, m/z =

38 c)typical procedure for the Heck reaction of 3g and indobenzene A stirred solution of 3g (87.4 mg, 0.2 mmol) in DMF (4 ml) was added Pd(OAc)2 (4.5 mg, 0.02 mmol), NaHCO3 (50.4 mg, 0.6 mmol) and Tetrabutylammonium chloride (TBAC, 56 mg, 0.2 mmol). The mixture was stirred at 80 for 24 h, after completion of the reaction, the reaction mixture was allowed to cool to room temperature, quenched with water and extracted with EtOAc. The organic layer was separated, dried over MgSO4 and the solvents were removed in vacuo. The residue was purified by silica gel chromatography using petroleum ether/dcm as the eluent to afford the desired 8 (87.4 mg, E/Z = 4:1, 85%) without loss of enantiopurity. Data and HPLC Spectra for 8: The product was obtained as a white acicular solid in 85% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 1.2 Hz, 1H), (m, 6H), (m, 3H), (m, 3H), 6.74 (d, J = 8.0 Hz, 1H), 6.10 (s, 1H), 3.76 (d, J = 13.2 Hz, 1H), 3.65 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = 26.2 Hz), 51.97, (d, JC, F = 1.8 Hz); 19 F NMR (376 MHz, CDCl3) δ ; 38

39 Enantiomeric excess: 96%, determined by HPLC (Chiralpak OD-H, hexane/i- PrOH = 90/10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. for C27H21BrF3O2 [M+H] + = , found = d) Typical procedure for [3+2] cycloaddition of 3g and aldoxime A stirred solution of 3g (87.4 mg, 0.2 mmol) and hydroximinoyl chloride (46.7 mg, 0.3 mmol) in dry THF (2 ml) was treated with diisopropylethylamine (DIPEA, 0.1 ml, 0.4 mmol). The mixture was stirred at room temperature for 2.5 h. Then, the solvent was evaporated in vacuo. The residue was purified by silica gel chromatography using petroleum ether/dcm (4:1 to 2:1) as an eluent to afford the desired 9 (101.2 mg, dr = 3:1, 91%) without loss of enantiopurity. Data and HPLC Spectra for 9: The product was obtained as a sticky oil in 91% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 1.6 Hz, 1H), (m, 2H), (m, 7H), (m, 3H), 6.44 (s, 1H), 3.45 (d, J = 17.2 Hz, 1H), 3.36 (s, 3H), 3.22 (d, J = 14.4 Hz, 1H), 3.06 (d, J = 14.4 Hz, 1H), 2.93 (d, J = 16.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , 39

40 130.52, , , , , , , , , , , 86.52, (q, JC, F = 26.4 Hz), 52.73, 43.91, 37.45; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak OD-H, hexane/i- PrOH = 90/10; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (ESI) m/z calcd. For C28H22BrF3NO3 [M+H] + = , found = e) Typical procedure for the oxidation and condensation with phenylhydrazine A solution of 3g (81.8 mg, 0.2 mmol) in dry dichloromethane (8 ml) was added Dess-Martin periodinane (127.2, 0.3 mmol) at 0 C. After stirring 10 min, the solvent was evaporated in vacuo. And the reaction mixture was quenched with saturated sodium bicarbonate and sodium thiosulfate was then added. After stirring for another 10 min, the biphasic mixture was extracted with ethyl acetate, the organic phase was washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column to afford the desired acrylaldehyde. To a solution of acrylaldehyde in ethanol (2 ml), 2,4-dinitrophenylhydrazine (47.6 mg, 40

41 0.24 mmol) and few drops of concentrated sulfuric acid was added. The mixture was stirred at room temperature for 2 h. After completion of the reaction (monitored by TLC), the residue washed with water twice and dried over anhydrous sodium sulfate filtered, concentrated, and purified by silica gel column to obtained the desired product 10 (267.1 mg, 92%) without loss of enantiopurity. Data and HPLC Spectra for 10: The product was obtained as a red solid in 91% yield; [α]d 25 = (c = 0.50, CHCl3); 1 H NMR (400 MHz, CDCl3) δ (s, 1H), 9.10 (d, J = 2.8 Hz, 1H), 8.31 (dd, J = 9.2, 2.4 Hz, 1H), 7.86 (d, J = 9.2 Hz, 1H), 7.63 (s, 1H), 7.56 (d, J = 1.6 Hz, 1H), 7.49 (d, J = 8.0 Hz, 1H), (m, 6H), 6.33 (s, 1H), 5.34 (s, 1H), 5.18 (s, 1H), 3.61 (d, J = 13.2 Hz, 1H), 3.25 (d, J = 13.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , (q, JC, F = Hz), , , , , , (q, JC, F = Hz), 30.90; 19 F NMR (376 MHz, CDCl3) δ ; Enantiomeric excess: 96%, determined by HPLC (Chiralpak OD-H+AD-H, hexane/i-proh = 80/20; flow rate 0.5 ml/min; 25 C; 254 nm), first peak: tr = min, second peak: tr = min; HRMS (EI) calcd for C26H18O4N4F3Br, m/z = (M + ); found, m/z =

42 8. Typical Procedure for synthesis the starting materials of 1 General Trifluoromethylation Procedure In a typical reaction [6], chalcones A (5 mmol) and TMSCF3 (6-7.5 mmol) were dissolved in 10 ml THF and cesium fluoride (38.0 mg, 0.25 mmol) was added directly at room temperature. The reaction was exothermic and the solution changed from colorless to yellowish brown. It was stirred at 25 for 4h, diluted with ethyl acetate (25 ml) and filtered. Removal of solvent at reduced pressure and the residue was purified directly by column chromatography on silica gel using petroleum ether as an eluent to afford pure trans-α-trifluoromethyl silyl ethers in >95% yield. Then, trans-αtrifluoromethyl silyl ethers were dissolved in MeOH (15mL) and treated with 6 M HCl slowly. It was stirred vigorously for 4 h-6 h at room temperature. After consumption of silyl ethers (monitored by TLC), the reaction mixture diluted with EtOAc. The organic layer was separated, dried over Na2SO4 and the solvents were removed in vacuo. The residue was purified by silica gel chromatography using PE/EA (15:1) as the eluent to afford the pure trans-α-trifluoromethyl allylic alcohols B in>95% yield. To a solution of B (x mmol) in DCM (10 ml), cooled to -78 C, then added BF3 Et2O ( equiv). directly. And 30 min later, turning off the refrigeration and warming to r.t. naturely. The reaction medium was stirred for 24 h, the solvent was then removed and the residue was purified directly by column chromatography on silica gel using pure petroleum ether as an eluent to afford 1-phenyl-3-(trifluoromethyl)-1Hindene or a mixture with 3-phenyl-1-(trifluoromethyl)-1H-indene which cannot be separated by column chromatography on silica gel easily. Noted: Under the room temperature for an extended period, compound 1 was isomerized into the more conjugated 1' slowly. 42

43 9. General Data for Starting Material of 1 and 4 1a 1-phenyl-3-(trifluoromethyl)-1H-indene The product was obtained as a white solid (x = 8.98 mmol, 1.65 g, 71%); 1 H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 7.2 Hz, 1H), (m, 6H), (m, 2H), (m, 1H), 4.72 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , (d, JC, F = 5.0 Hz), , , (q, JC, F = 34.1 Hz), , , , , , , (q, JC, F = Hz), , 55.43; 19 F NMR (376 MHz, CDCl3) δ a 3-phenyl-1-(trifluoromethyl)-1H-indene The product was obtained as a white solid (x = 8.49 mmol, 1.79 g, 81%) in 81% yield; 1 H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 7.6 Hz, 1H), (m, 3H), (m, 4H), (m, 1H), 6.44 (d, J = 2.0 Hz, 1H), 4.27 (m, 1H); 13 C NMR (100 MHz, CDCl3) δ , , (d, JC, F = 1.8 Hz), , , , , , , (q, JC, F = Hz), , (d, JC, F = 2.8 Hz), , (q, JC, F = 29.4 Hz); 19 F NMR (376 MHz, CDCl3) δ a:1a =1:1 1-phenyl-3-(trifluoromethyl)-1H-indene & 3-phenyl-1-(trifluoromethyl)-1Hindene 1 H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 7.6 Hz, 1H), (m, 4H),

44 (m, 4H), (m, 7H), (m, 2H), (m, 1H), 6.45 (d, J = 2.0 Hz, 1H), 4.75 (s, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , (q, JC, F = 5.0 Hz), (d, JC, F = 1.8 Hz), , , , (q, JC, F = 34.1 Hz), , , , , , , , , , , (q, JC, F = Hz), , (d, JC, F = 2.1 Hz), , (q, JC, F = Hz), , , 55.48, (q, JC, F = 29.5 Hz); 19 F NMR (376 MHz, CDCl3) δ , b:1b =1:0 6-methyl-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-methyl-3-phenyl-1-(trifluo -romethyl)-1h-indene The product was obtained as a white solid (x = 4.17 mmol, 941 mg, 82%); 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.6 Hz, 1H), (m, 3H), 7.19 (d, J = 7.6 Hz, 1H), (m, 3H), 6.96 (d, J = 1.6 Hz, 1H), 4.69 (s, 1H), 2.36 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 5.0 Hz), , , , (q, JC, F = 34.0 Hz), , , , , , (q, JC, F = Hz), , 55.23, (d, JC, F = 0.6 Hz); 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C17H13F3, m/z = (M + ); found, m/z = c:1c =1:2 6-methoxy-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-methoxy-3-phenyl-1-(trif -luoromethyl)-1h-indene The product was obtained as a white solid (x = 3.67 mmol, 680 mg, 64%); 1 H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.2 Hz, 4H), (m, 8H), (m, 5H), 7.16 (d, J = 8.0 Hz, 1H), 7.07 (d, J = 4.8 Hz, 3H), 7.01 (s, 1H), 6.93 (dd, J = 8.4, 1.6 Hz, 2H), 6.81 (dd, J = 8.4, 2.0 Hz, 1H), 6.28 (d, J = 1.6 Hz, 2H), 4.66 (s, 1H), 4.19 (q, J = 9.2 Hz, 2H), 3.85 (s, 6H), 3.83 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , 44

45 158.85, , (d, JC, F = 4.5 Hz), (d, JC, F = 4.5 Hz), , , , , , (q, JC, F = 33.6 Hz), , , , , , , (q, JC, F = Hz), , (d, JC, F = 2.7 Hz), (q, JC, F = Hz), , , , , , (d, JC, F = 4.5 Hz), 54.79, (q, JC, F = 29.1 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C17H13OF3, m/z = (M + ); found, m/z = d:1d =1:5 1- phenyl-3,6-bis(trifluoromethyl)-1h-indene & 3-phenyl-1,5-bis(trifluorometh -yl)-1h-indene The product was obtained as a white powder solid (x = 3.67 mmol, 600 mg, 50%); 1 H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 8.4 Hz, 10H), (m, 17H), (m, 16H), 7.34 (d, J = 6.4 Hz, 3H), 7.19 (s, 1H), 7.10 (d, J = 6.0 Hz, 2H), 6.55 (s, 5H), 4.81 (s, 1H), 4.33 (q, J = 9.2 Hz, 5H); 13 C NMR (100 MHz, CDCl3) δ , , , (q, JC, F = 4.4 Hz), , (q, JC, F = 1.7 Hz), , , (q, JC, F = 32.0 Hz), , , , , , , (d, JC, F = 2.4 Hz), (q, JC, F = Hz), , (q, JC, F = 3.8 Hz), (q, JC, F = Hz), (q, JC, F = 3.8 Hz), (d, JC, F = 3.7 Hz), , (q, JC, F = 3.7 Hz), 55.66, (q, JC, F = 29.8 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C17H10F6, m/z = (M + ); found, m/z = e:1e =0:1 6-fluoro-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-fluoro-3-phenyl-1-(trifleoro -methyl)-1h-indene 45

46 The product was obtained as a white powder solid (x = 3.70 mmol, 736 mg, 72%); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 3H), (m, 1H), (m, 1H), 6.48 (d, J = 2.0 Hz, 1H), 4.20 (q, J = 9.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , (d, JC, F = 2.9 Hz), (d, JC, F = 8.9 Hz), (d, JC, F = 4.4 Hz), , , , (d, JC, F = 2.1 Hz), (q, JC, F = Hz), (d, JC, F = 9.4 Hz), (d, JC, F = 23.1 Hz), (d, JC, F = 24.1 Hz), (q, JC, F = 29.5 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C16H10F4, m/z = (M + ); found, m/z = f:1f =1.5:1 6-chloro-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-chloro-3-phenyl-1-(trifluor -omethyl)-1h-indene The product was obtained as a white powder solid (x = 4.93 mmol, 983 mg, 68%); 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 4.5H), (m, 8.5 H), (m, 3H), 7.03 (s, 1.5H), 6.49 (s, 1H), 4.73 (s, 1.5H), 4.25 (q, J = 9.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , (d, JC, F = 4.4 Hz), (d, JC, F = 1.4 Hz), , , , (q, JC, F = 34.5 Hz), , , , , , , , , , , , (q, JC, F = Hz), , , (q, JC, F = Hz), , , 55.40, (q, JC, F = 29.6 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C16H10ClF3, m/z = (M + ); found, m/z = g:1g =0:1 6-bromo-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-bromo-3-phenyl-1-(trifluo -romethyl)-1h-indene 46

47 The product was obtained as a white powder solid (x = 4.96 mmol, 1.15 g, 68%); 1 H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 1.6 Hz, 1H), (m, 2H), (m, 5H), 6.46 (d, J = 2.0 Hz, 1H), 4.22 (q, J = 8.8, 1H); 13 C NMR (100 MHz, CDCl3) δ , , (d, JC, F = 1.9 Hz), , , , , , , (q, JC, F = Hz), , , (q, JC, F = 29.6 Hz); 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C16H10F3Br, m/z = (M + ); found, m/z = h:1h =1.5:1 6-iodo-1-phenyl-3-(trifluoromethyl)-1H-indene & 5-iodo-3-phenyl-1-(trifluoro -methyl)-1h-indene The product was obtained as a white powder solid (x = 2.38 mmol, 583 mg, 63%); 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 0.8 Hz, 1H), (m, 2H), 7.63 (s, 1.5H), (m, 2H), (m, 4.5H), (m, 6H), 7.08 (m, 3H), 6.97 (t, J = 1.6 Hz, 1H), 6.42 (d, J = 2.4 Hz, 1H), 4.70 (s, 1.5H), 4.21 (q, J = 9.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , (q, JC, F = 4.1 Hz), (d, JC, F = 2.0 Hz), , , , , (q, JC, F = 34.4 Hz), , , , , , , , , , , (d, JC, F = 2.3 Hz), (q, JC, F = Hz), , (q, JC, F = Hz), 94.44, 92.57, 55.36, (q, JC, F = 27.6 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C16H10F3I, m/z = (M + ); found, m/z = i:1i =1:5 4-methyl-1-phenyl-3-(trifluoromethyl)-1H-indene & 7-methyl-3-phenyl-1-(trileor -omethyl)-1h-indene 47

48 The product was obtained as a white powder solid (x = 4.90 mmol, 1.06 g, 79%); 1 H NMR (500 MHz, CDCl3) δ (m, 10H), (m, 10H), (m, 10H), (m, 6H), (m, 2H), (m, 9H), (m, 2H), 6.39 (d, J = 2.0 Hz, 5H), 4.62 (s, 1H), (m, 5H), 2.55 (s, 3H), 2.48 (s, 15H); 13 C NMR (125 MHz, CDCl3) δ , , , (q, JC, F = 6.3 Hz), , (d, JC, F = 1.6 Hz), , , , (q, JC, F = 33.6 Hz), , , , , , , , , , , , (q, JC, F = Hz), (q, JC, F = 3.0 Hz), (q, JC, F = Hz), , , 54.62, (q, JC, F = 29.0 Hz), (q, JC, F = 3.8 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C17H13F3, m/z = (M + ); found, m/z = j:1j =1:0 5,7-dimethyl-1-phenyl-3-(trifluoromethyl)-1H-indene & 4,6-dimethyl-3-phenyl-1- (trifluoromethyl)-1h-indene The product was obtained as a white powder solid (x = 4.00 mmol, 983 mg, 68%); 1 H NMR (400 MHz, CDCl3) δ (m, 4H), 7.02 (dd, J = 7.6, 1.2 Hz, 2H), 6.90 (d, J = 4.0 Hz, 2H), 4.66 (s, 1H), 2.41 (s, 3H), 2.00 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 3.9 Hz), , , , , (q, JC, F = 33.8 Hz), , , , , (q, JC, F = Hz), , 54.86, (d, JC, F = 2.2 Hz), 18.61; 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C18H15F3, m/z = (M + ); found, m/z = k:1k =21:1 5-phenyl-7-(trifluoromethyl)-5H-indeno[5,6-d][1,3]dioxole & 7-phenyl-5-(trifluor 48

49 -omethyl)-5h-indeno[5,6-d][1,3]dioxole The product was obtained as a white powder solid (x = 3.88 mmol, 1.03 g, 87%); 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 2H), 7.00 (s, 1H), 6.91 (s, 1H), 6.75 (s, 1H), 5.96 (d, J = 5.6 Hz, 2H), 4.59 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , , (d, JC, F = 4.9 Hz), , (q, JC, F = 34.0 Hz), , , , , (q, JC, F = Hz), , , , 55.21; 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C17H11O2F3, m/z = (M + ); found, m/z = l:1l =0:1 5,6-dimethoxy-1-phenyl-3-(trifluoromethyl)-1H-indene & 5,6-dimethoxy-3- phenyl-1-(trifluoromethyl)-1h-indene The product was obtained as a white powder solid (x = 3.82 mmol, 1.02 g, 83%); 1 H NMR (400 MHz, CDCl3) δ (m, 2H), 7.49 (t, J = 7.6 Hz, 2H), (m, 1H), 7.23 (s, 1H), 7.08 (s, 1H), 6.32 (d, J = 2.0 Hz, 1H), (m, 1H), 3.95 (s, 3H), 3.89 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , , , , , (d, JC, F = 1.9 Hz), , , , (q, JC, F = Hz), (d, JC, F = 2.5 Hz), , , (d, JC, F = 3.0 Hz), (d, JC, F = 3.0 Hz), (q, JC, F = 26.9 Hz); 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C18H15O2F3, m/z = (M + ); found, m/z = m:1m =1:8 3-phenyl-1-(trifluoromethyl)-3H-cyclopenta[a]naphthalene & 3-phenyl-1-(trifluo -romethyl)-1h-cyclopenta[a]naphthalene 49

50 The product was obtained as a white powder solid (x = 3.80 mmol, 1.07 g, 91%); 1 H NMR (400 MHz, CDCl3) δ 8.38 (d, J = 8.8 Hz, 1H), 8.16 (d, J = 8.4 Hz, 8H), 7.89 (d, J = 8.4 Hz, 16H), 7.76 (d, J = 8.4 Hz, 1H), 7.68 (d, J = 8.4 Hz, 8H), (m, 16H), (m, 8H), (m, 32H), (m, 3H), 7.27 (d, J = 7.2 Hz, 4H), 7.21 (s, 1H), (m, J = 7.5, 2H), 6.52 (d, J = 2.0 Hz, 8H), 4.74 (s, 1H), (m, 8H); 13 C NMR (100 MHz, CDCl3) δ 13 C NMR (100 MHz, CDCl3) δ , , (d, JC, F = 6.2 Hz), , , (d, JC, F = 1.8 Hz), , , (d, JC, F = 3.4 Hz), , , , , , , , , , , , , , , , (q, JC, F = Hz), (d, JC, F = 0.9 Hz), , , (q, JC, F = 4.3 Hz), , , 55.54, (q, JC, F = 29.0 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C20H13F3, m/z = (M + ); found, m/z = n:1n =1:0 1- phenyl-3-(trifluoromethyl)-1h-cyclopenta[a]naphthalene & 1-phenyl-3-(trifle -oromethyl)-3h-cyclopenta[a]naphthalene The product was obtained as a white powder solid (x = 4.48 mmol, 1.02 mg, 73%); 1 H NMR (400 MHz, CDCl3) δ 7.89 (t, J = 7.2 Hz, 2H), 7.71 (d, J = 8.4 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 1H), (m, 3H), (m, 3H), 5.01 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 5.1 Hz), , , (q, JC, F = 34.2 Hz), , , , , , , , , , (q, JC, F = Hz), , 55.46; 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C20H13F3, m/z = (M + ); 50

51 found, m/z = o:1o =25:1 1-(p-tolyl)-3-(trifluoromethyl)-1H-indene & 3-(p-tolyl)-1-(trifluoromethyl)-1Hindene The product was obtained as a white solid (x = 3.00 mmol, 470 mg, 57%); 1 H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 7.2 Hz, 1H), 7.37 (t, J = 7.2 Hz, 1H), (m, 2H), 7.12 (d, J = 7.6 Hz, 2H), 7.00 (s, 2 H), 6.99 (s, 1H), 4.71 (s, 1H), 2.34 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 4.9 Hz), , , (q, JC, F = 34.0 Hz), , , , , , , (q, JC, F = Hz), , 55.12, (d, JC, F = 1.2 Hz); 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C17H13F3, m/z = (M + ); found, m/z = p:1p =1:0 1-(4-chlorophenyl)-3-(trifluoromethyl)-1H-indene & 3-(4-chlorophenyl)-1-(trifl -uoromethyl)-1h-indene The product was obtained as a white solid (x = 1.38 mmol, 366 mg, 90%); 1 H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 7.2 Hz, 1H), (m, 1H), (m, 4H), 7.02 (d, J = 8.4 Hz, 2H), 6.96 (t, J = 1.6 Hz, 1H), 4.68 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 5.0 Hz), , (q, JC, F = 34.2 Hz), , , , , , , , (q, JC, F = Hz), , 54.67; 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C16H10ClF3, m/z = (M + ); found, m/z = q:1q =12:1 1-(4-bromophenyl)-3-(trifluoromethyl)-1H-indene & 3-(4-bromophenyl)-1-(trifleo 51

52 -romethyl)-1h-indene The product was obtained as a white solid (x = 2.62 mmol, 675 mg, 72%); 1 H NMR (400 MHz, CDCl3) δ (dd, J = 7.6, 0.4 Hz, 1H), (m, 3H), (m, 2H), (m, 3H), 4.66 (t, J = 2.0, 1H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 5.0 Hz), , , (q, JC, F = 34.1 Hz), , , , , , , (q, JC, F = Hz), , 54.71; 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C16H10F3Br, m/z = (M + ); found, m/z = r:1r =2.5:1 4-(3-(trifluoromethyl)-1H-inden-1-yl)benzonitrile & 4-(1-(trifluoromethyl)-1Hinden-3-yl)benzonitrile The product was obtained as a white solid (x = 3.59 mmol, 730 mg, 71%); 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.0 Hz, 2H), (m, 3H), (m, 7.5 H), 7.48 (dd, J = 15.6, 7.2 Hz, 2H), (m, 4H), (m, 4H), 7.25 (s, 1H), 7.21 (d, J = 8.4 Hz, 5H), 6.97 (t, J =1.6 Hz, 2.5 H), 6.53 (d, J = 2.0 Hz, 1H), 4.77 (s, 2.5H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , (q, JC, F = 34.3 Hz), , (d, JC, F = 1.8 Hz), (q, JC, F = 0.9 Hz), (q, JC, F = 4.8 Hz), , , , , , , , (q, JC, F = Hz), , , , (q, JC, F = Hz), , , , , , 55.02, (q, JC, F = 29.5 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C17H10NF3, m/z = (M + ); found, m/z = s:1s >50:1 52

53 1-(3-bromophenyl)-3-(trifluoromethyl)-1H-indene & 3-(3-bromophenyl)-1-(trifle -oromethyl)-1h-indene The product was obtained as a white solid (x = 3.00 mmol, 825 mg, 81%); 1 H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.6 Hz, 1H), (m, 2H), 7.30 (d, J = 4.0 Hz, 2H), 7.25 (s, 1H), 7.18 (t, J = 8.0 Hz, 1H), 7.03 (d, J = 8.0 Hz, 1H), 6.98 (s, 1H), 4.68 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 4.8 Hz), , (d, JC, F = 0.8 Hz), (q, JC, F = 34.2 Hz), , , , , , , , , (q, JC, F = Hz), , 54.86; 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C16H10F3Br, m/z = (M + ); found, m/z = t:1t =1:0 1-(2-bromophenyl)-3-(trifluoromethyl)-1H-indene & 3-(2-bromophenyl)-1-(trifl -uoromethyl)-1h-indene The product was obtained as a white solid (x = 3.00 mmol, 822 mg, 81%); 1 H NMR (400 MHz, CDCl3) δ (m, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.40 (t, J = 7.2 Hz, 2H), 7.30 (t, J = 7.2 Hz, 1H), (m, 2H), 7.05 (s, 1H), (m, 1H), 5.36 (s, 1H); 13 C NMR (100 MHz, CDCl3) δ , (q, JC, F = 4.9 Hz), , , (q, JC, F = 34.1 Hz), , , , , , , , , (q, JC, F = Hz), , 54.60; 19 F NMR (376 MHz, CDCl3) δ ; HRMS (EI) calcd for C16H10F3Br, m/z = (M + ); found, m/z = u:1u =1:1 1-([1,1'-biphenyl]-4-yl)-3-(trifluoromethyl)-1H-indene & 3-([1,1'-biphenyl]-4-yl)- 53

54 1-(trifluoromethyl)-1H-indene The product was obtained as a white solid (x = 2.90 mmol, 703 mg, 72%); 1 H NMR (400 MHz, CDCl3) δ (m, 8H), (m, 11H), (m, 5H), 7.18 (d, J = 8.0 Hz, 2H), 7.06 (s, 1H), 6.50 (d, J = 2.0 Hz, 1H), 4.79 (s, 1H), 4.29 (q, J = 8.4 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , (d, JC, F = 5.2 Hz), , , , (d, JC, F = 1.6 Hz) , , (q, JC, F = 33.9 Hz), , , , , , , , , , , , , , , (q, JC, F = Hz), , , , , (q, JC, F = Hz), , , 55.11, (q, JC, F = 29.5 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C22H15F3, m/z = (M + ); found, m/z = v:1v =1:2.3 2-(3-(trifluoromethyl)-1H-inden-1-yl)naphthalene & 2-(1-(trifluoromethyl)-1Hinden-3-yl)naphthalene The product was obtained as a white solid (x = 2.23 mmol, 371 mg, 54%); 1 H NMR (400 MHz, CDCl3) δ 8.13 (s, 2.3H), 7.97 (d, J = 8.4 Hz, 2.3H), (m, 4.3H), (m, 2H), (m, 6.6H), 7.69 (d, J = 7.6 Hz, 2.3H), 7.63 (d, J = 7.6 Hz, 1H), (m, 4.6H), (m, 4.3H), (m, 3.3H), (m, 2.3H), 7.10 (t, J = 2.0 Hz, 1H), 7.03 (dd, J = 8.4, 1.6 Hz, 1H), 6.57 (d, J = 2.4 Hz, 2.3H), 4.90 (s, 1H), (m, 2.3H); 13 C NMR (100 MHz, CDCl3) δ , , , (q, JC, F = 4.9 Hz), (d, JC, F = 1.9 Hz), (d, JC, F = 0.5 Hz), (q, JC, F = 34.0 Hz), , , , , , , , 54

55 128.46, , , , , , , , , , , , , (q, JC, F = Hz), , , , , , , , (q, JC, F = Hz), , , 55.60, (q, JC, F = 29.4 Hz); 19 F NMR (376 MHz, CDCl3) δ , ; HRMS (EI) calcd for C20H13F3, m/z = (M + ); found, m/z = methyl 1-(4-methoxyphenyl)-1H-indene-3-carboxylate The product was obtained as a white solid in 75% yield; 1 H NMR (300 MHz, CDCl3) δ 7.74 (d, J = 7.2 Hz, 1H), (m, 3H), (m, 2H), (m, 2H), 6.55 (d, J = 2.4 Hz, 1H), 4.56 (d, J = 2.1 Hz, 1H), 3.88 (s, 3H), 3.78 (s, 3H); MS (EI): m/z (%) = 280 (M +, 46.68), 221 (100). The analytical data match those reported in the literature. [3] 55

56 10. X-ray crystal structure for References [1] Yoshida, M.; Ohmiya, H.; Sawamura, M. J. Am. Chem. Soc. 2012, 134, [2] Radix-Large, S.; Kucharski, S.; Langlois, B. R. Synthesis 2004, 3, 456. [3] Park, E. J.; Kim, S. H.; Chang, S. J. Am. Chem. Soc. 2008, 130, [4] a) Langer, P. Angew. Chem. Int. Ed. 2000, 39, 3049; b) Pautigny, C.; Jeulin, S.; Ayad, T.; Zhang, Z.; Gene t, J. -P.; Ratovelomanana-Vidal, V. Adv. Synth. Catal. 2008, 350, [5] (a) Zhang, Z. -M.; Chen, P.; Li, W.; Niu, Y.; Zhao, X. -L.; Zhang, J. Angew. Chem. Int. Ed. 2014, 53, 4350; (b) Su, X.; Zhou, W.; Li, Y.; Zhang, J. Angew. Chem. Int. Ed. 2015, 54, 6874; (c) Zhou, W.; Su, X.; Tao, M.; Zhu, C.; Zhao, Q.; Zhang, J. Angew. Chem. Int. Ed. 2015, 54, 14853; (d) Zhou, W.; Chen, P.; Tao, M.; Su, X.; Zhao, Q.; Zhang, J. Chem. Commun. 2016, 52, 7612; (e) Chen, P.; Yue, Z.; Zhang, J.; Lv, X.; Wang, L.; Zhang, J. Angew. Chem. Int. Ed. 2016, 55, [6] Singh, R. P.; Kirchmeier, R. L.; Shreeve, J. M. Org. Lett. 1999, 1,