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

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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 c thchuang@mail.cmu.edu.tw a School of Pharmacy, China Medical University, Taichung, 40402, Taiwan, ROC b Department of Cosmetic Science, Vanung University, No.1 Van-Nung Rd., Chung-Li, Tao-Yuan 32045, Taiwan, ROC c Department of Chemistry, Kakatiya University, Warangal, India Table of contents Experimental procedures and characterization References for known compounds Page S2-S5 S5 1 H and 13 C NMR spectra S6 following S1

Experimental General All reagents were purchased and used without further purification. Nuclear magnetic resonance spectra were recorded on 300 MHz and 400 MHz FT-NMR spectrometers; all chemical shifts were reported in ppm from tetramethylsilane as an internal standard. Column chromatography was carried out using 230 400 mesh silica gel and 70 230 mesh neutral aluminum oxide. (E)-[2-13 C]Cinnamic acid (3a- 13 C). A mixture of [2-13 C]malonic acid (0.21 g, 2 mmol), benzaldehyde (0.46 g, 4 mmol) and a catalytic amount of piperidine in dry pyridine (10 ml) was heated at 90 o C for 9h. After cooling, the resulting solution was poured to ice-water, acidified with conc. HCl and allowed to precipitate a white solid. The solid was filtered and washed with cold water to give pure 3a- 13 C. Yield 51%; white solid, mp 136 137 o C (hexane-ch 2 Cl 2 ) (lit. 1 mp 130 131 o C). 1 H NMR (CDCl 3 ) δ 6.46 (1H, dd, J = 162.8, 16.0 Hz), 7.41 (3H, m), 7.56 (2H, m), 7.80 (1H, dd, J = 16.0, 2.9 Hz); 13 C NMR (CDCl 3 ) δ 117.3, 128.3 (2 C, d, J = 5 Hz), 128.9 (2 C), 130.7, 134.0, 147.1 (1 C, d, J = 70 Hz), 172.5 (1 C, d, J = 74 Hz); IR (KBr) 1678 cm -1 ; EIMS m/z (rel int) 149 (78, M + ); HREIMS m/z calcd for 12 C 8 13 CH 7 O 2 : 149.0557, found: 149.0550. General Procedure for the Preparation of acryloyl azides 4. To a stirred solution of acrylic acid 3a-d, 3j or 3k (10 mmol) in CH 2 Cl 2 (50 ml) at room temperature was added oxalyl chloride (2.54 g, 20 mmol), and the mixture was stirred at room temperature for 5h. The resulting mixture concentrated under reduced pressure to afford acryloyl chloride quantitatively which was used S2

directly without further purification in the following reaction. The acryloyl chloride was added immediately into a suspension of NaN 3 (1.95 g, 30 mmol) in dry acetone (20 ml) on an ice bath. The reaction mixture was stirred gently for 2h at room temperature and filtered. The solvent was evaporated in vacuo, and the residue was purified by column chromatography over silica gel eluting with hexane-etoac (30:1) to yield pure acryloyl azide 4a-d 2, 4j or 4k. A mixture of acrylic acid 3e-g or 3i and oxalyl chloride in toluene was heated at 80 o C for 5h. Subsequently, a similar procedure as described above was used to prepare acryloyl azide 4e-g 2 or 4i. In the case of 4h, the mixture of acrylic acid 3h and oxalyl chloride in DMF was heated at 80 o C for 5h. After cooling, NaN 3 was added directly to the above solution, and the reaction mixture was stirred gently for 2h at room temperature to obtain acryloyl azide 4h. The full spectral data of 4a and 4h-k were described as follows. (E)-Cinnamoyl azide (4a). Yield 97%; white solid. 1 H NMR (300MHz, CDCl 3 ) δ 6.43 (1H, d, J = 16.0 Hz), 7.39 (3H, m), 7.53 (2H, m), 7.75 (1H, d, J = 16.0 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 119.1, 128.5, 129.0, 131.1, 133.8, 146.7, 172.1; IR (KBr) 2146, 1687 cm -1 ; EIMS m/z (rel int) 173 (43, M + ); HREIMS m/z calcd for C 9 H 7 N 3 O: 173.0589, found:173.0589 [M] +. (E)-[2-13 C]Cinnamoyl azide (4a- 13 C). Yield 93%; white solid. 1 H NMR (300MHz, CDCl 3 ) δ 6.42 (1H, dd, J = 163.1, 15.9 Hz), 7.41 (3H, m), 7.53 (2H, m), 7.75 (1H, dd, J = 15.9, 2.9 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 119.0, 128.5 (2 C, d, J = 5 Hz), 129.0 (2 C), 131.1, 133.8, 146.7 (1 S3

C, d, J = 70 Hz), 172.0 (1 C, d, J = 73 Hz); IR (KBr) 2149, 1678 cm -1 ; FABMS m/z (rel int) 174 (36, M + ); HRFABMS m/z calcd for 12 C 8 13 CH 7 N 3 O: 174.0667, found: 174.0670 [M] +. (E)-3-(3-Pyridyl)acryloyl azide (4h). Yield 90%; pale yellow solid. 1 H NMR (300MHz, CDCl 3 ) δ 6.50 (1H, d, J = 16.0 Hz), 7.36 (1H, dd, J = 8.0, 4.8 Hz), 7.75 (1H, d, J = 16.0 Hz), 7.86 (1H, dt, J = 8.0, 1.6 Hz), 8.65 (1H, dd, J = 4.8, 1.6 Hz), 8.76 (1H, d, J = 1.6 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 121.1, 123.8, 129.6, 134.5, 142.8, 150.1, 151.7, 171.5; IR (KBr) 2149, 1680 cm -1 ; FABMS m/z (rel int) 175 (69, [MH] + ); HRFABMS m/z calcd for C 8 H 7 N 4 O: 175.0620, found: 175.0621 [MH] +. (E)-3-(Ethoxycarbonyl)acryloyl azide (4i). Yield 60%; colorless liquid. 1 H NMR (300MHz, CDCl 3 ) δ 1.33 (3H, t, J = 7.1 Hz), 4.28 (2H, q, J = 7.1 Hz), 6.80 (1H, d, J = 15.8 Hz), 6.90 (1H, d, J = 15.8 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 13.9, 61.5, 133.7, 134.8, 164.3, 170.7; IR (KBr) 2964, 2140, 1698, 1644 cm -1 ; FABMS m/z (rel int) 170 (12, [MH] + ); HRFABMS m/z calcd for C 6 H 8 N 3 O 3 : 170.0566, found: 170.0569 [MH] +. (E)-2-Hexenoyl azide (4j). Yield 88%; colorless liquid. 1 H NMR (300MHz, CDCl 3 ) δ 0.94 (3H, t, J = 7.4 Hz), 1.50 (2H, sextet, J = 7.4 Hz), 2.22 (2H, q, J = 7.4 Hz), 5.86 (1H, d, J = 15.5 Hz), 7.07 (1H, dt, J = 15.5, 7.4 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 13.5, 21.0, 34.4, 122.7, 152.1, 171.7; IR (KBr) 2141, 1699 cm -1 ; EIMS m/z (rel int) 111 (10, [M-N 2 ] + ); HREIMS m/z calcd for C 6 H 9 NO: 111.0684, found: 111.0684 [M-N 2 ] +. (E)-3-Butoxyacryloyl azide (4k). Yield 87%; colorless liquid. 1 H NMR (300MHz, CDCl 3 ) δ 0.95 (3H, t, J = 7.4 Hz), 1.42 (2H, sextet, J = 7.4 Hz), 1.70 (2H, quintet, J = 7.4 Hz), 3.90 (2H, t, J = 7.4 Hz), 5.23 (1H, d, J = 12.4 Hz), 7.68 (1H, d, J = 12.4 Hz); 13 C NMR (75MHz, CDCl 3 ) δ 13.6, S4

18.9, 30.8, 71.7, 98.4, 164.7, 172.2; IR (KBr) 2141, 1690 cm -1 ; FABMS m/z (rel int) 170 (7, [MH] + ); HRFABMS m/z calcd for C 7 H 12 N 3 O 2 : 170.0930, found: 170.0931 [MH] +. References 1. Hano, Y.; Shimazaki, M.; Nomura, T.; Ueda, S. Heterocycles 1999, 50, 989-994. 2. Chuang, T. H.; Wu, P. L. J. Chin. Chem. Soc. 2006, 53, 413-420. S5

O 13 C OH 3a- 13 C 1 H NMR (300MHz, CDCl 3) S6

O 13 C OH 3a- 13 C 13 C NMR (75MHz, CDCl 3) S7

N 3 O 4a 1 H NMR (300MHz, CDCl 3) S8

N 3 O 4a 13 C NMR (75MHz, CDCl 3) S9

O 13 C N 3 4a- 13 C 1 H NMR (300MHz, CDCl 3) S10

O 13 C N 3 4a- 13 C 13 C NMR (75MHz, CDCl 3) S11

N 3 O 4h N 1 H NMR (300MHz, CDCl 3) S12

N 3 O 4h N 13 C NMR (75MHz, CDCl 3) S13

O EtO 2 C N 3 4i 1 H NMR (300MHz, CDCl 3) S14

O EtO 2 C N 3 4i 13 C NMR (75MHz, CDCl 3) S15

N 3 O 4j 1 H NMR (300MHz, CDCl 3) S16

N 3 O 4j 13 C NMR (75MHz, CDCl 3) S17

O O N 3 4k 1 H NMR (300MHz, CDCl 3) S18

O O N 3 4k 13 C NMR (75MHz, CDCl 3) S19

N 5a 1 H NMR (300MHz, CDCl 3) S20

N 5a 13 C NMR (75MHz, CDCl 3) S21

13 C 13 C N 13 C 5a- 13 C 1 H NMR (300MHz, CDCl 3) S22

13 C 13 C N 13 C 5a- 13 C 13 C NMR (75MHz, CDCl 3) S23

OCH 3 N 5b H 3 CO 1 H NMR (300MHz, CDCl 3) S24

OCH 3 N 5b H 3 CO 13 C NMR (75MHz, CDCl 3) S25

OCH 3 N 5c H 3 CO 1 H NMR (300MHz, CDCl 3) S26

OCH 3 N 5c H 3 CO 13 C NMR (75MHz, CDCl 3) S27

OCH OCH 3 3 N 5d 1 H NMR (300MHz, CDCl 3) S28

OCH OCH 3 3 N 5d 13 C NMR (75MHz, CDCl 3) S29

NO 2 N 5e O 2 N 1 H NMR (300MHz, DNSO-d 6) S30

NO 2 N 5e O 2 N 13 C NMR (75MHz, DMSO-d 6) S31

NO 2 N 5f O 2 N 1 H NMR (300MHz, CDCl 3) S32

NO 2 N 5f O 2 N 13 C NMR (75MHz, CDCl 3) S33

NO NO 2 2 N 5g 1 H NMR (300MHz, CDCl 3) S34

NO NO 2 2 N 5g 13 C NMR (75MHz, CDCl 3) S35

N N 5h N 1 H NMR (300MHz, CDCl 3) S36

N N 5h N 13 C NMR (75MHz, CDCl 3) S37

EtO 2 C CO 2 Et N 5i 1 H NMR (300MHz, CDCl 3) S38

EtO 2 C CO 2 Et N 5i 13 C NMR (75MHz, CDCl 3) S39

N 5j 1 H NMR (300MHz, CDCl 3) S40

N 5j 13 C NMR (75MHz, CDCl 3) S41

N 6a 1 H NMR (300MHz, CDCl 3) S42

N 6a 13 C NMR (75MHz, CDCl 3) S43

13 C 13 C N 13 C 6a- 13 C 1 H NMR (400MHz, CDCl 3) S44

S45

13 C 13 C N 13 C 6a- 13 C 13 C NMR (100MHz, CDCl 3) S46

OCH 3 OCH 3 N 6b H 3 CO 1 H NMR (300MHz, CDCl 3) S47

OCH 3 OCH 3 N 6b H 3 CO 13 C NMR (75MHz, CDCl 3) S48

OCH 3 OCH 3 N 6c H 3 CO 1 H NMR (300MHz, CDCl 3) S49

OCH 3 OCH 3 N 6c H 3 CO 13 C NMR (75MHz, CDCl 3) S50

OCH OCH 3 3 N OCH 3 6d 1 H NMR (300MHz, CDCl 3) S51

OCH OCH 3 3 N OCH 3 6d 13 C NMR (75MHz, CDCl 3) S52

N 6j 1 H NMR (300MHz, CDCl 3) S53

N 6j 13 C NMR (75MHz, CDCl 3) S54

O N 7 O 1 H NMR (300MHz, CDCl 3) S55

O N 7 O 13 C NMR (75MHz, CDCl 3) S56

1 H NMR (300MHz, CDCl 3) H N O NH 8a S57

13 C NMR (75MHz, CDCl 3) H N O NH 8a S58

1 H NMR (400MHz, DMSO-d 6) H N O 9a S59

13 C NMR (100MHz, DMSO-d 6) H N O 9a S60

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