Silver-catalyzed decarboxylative acylfluorination of styrenes in aqueous media

Transcription

1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Silver-catalyzed decarboxylative acylfluorination of styrenes in aqueous media Hua Wang, Li-Na Guo and Xin-Hua Duan* Department of Chemistry, School of Science and ME Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi an Jiaotong University, Xi an , China Table of Contents General Information S2 Starting Materials S2 General Procedure for the Decarboxylative Acylfluorination of Styrenes S3 with -xocarboxylic Acids Characterization of Products 3 S4 Characterization of Products 4 S8 Investigation of the Reaction chanism S12 Reference S14 1 H NMR and 13 C NMR Spectra of the Products 3 S15 1 H NMR and 13 C NMR Spectra of the Products 4 S33 S1

2 General Information All reactions were carried out under an atmosphere of nitrogen with strict exclusion of air. Column chromatography was carried out on silica gel. 1 H NMR and 13 C NMR spectra were recorded on a Bruker Advance III-400 in solvents as indicated. Chemical shift are reported in ppm from CDCl 3 using TMS as internal standard. IR spectra were recorded on a Bruker Tensor 27 spectrometer and only major peaks are reported in cm -1. HRMS were obtained on a Q-T micro spectrometer. Starting Materials Styrenes 1 were purchased from TCI, Alfa or Acros. Phenylglyoxylic acid 2a was purchased from Sigma-Aldrich. ther -oxocarboxylic acids 2 were prepared from the corresponding methyl ketones according to the reported procedure. 1 All of other commercially available compounds were used without further purification. S2

3 General Procedure for the Decarboxylative Acylfluorination of Styrenes with -xocarboxylic Acids Ar R 1 + R H AgN 3 (20 mol%) Selectfluor (1.5 equiv.) Na 2 S 4 (1 equiv.) acetone/h 2 (1:1), rt or 4 A 10 ml oven-dried Schlenk-tube was charged with AgN 3 (6.8 mg, 20 mol %), - xocarboxylic Acids (2, 0.3 mmol, 1.5 equiv.), Selectfluor (0.3 mmol, 1.5 equiv.), and Na 2 S 4 (0.2 mmol, 1.0 equiv.). The tube was evacuated and backfilled with nitrogen (three times). Styrenes (1, 0.2 mmol, 1.0 equiv.) in acetone/h 2 (1:1, 1 ml) were added by syringe under nitrogen. The tube was then sealed and the mixture was stirred for 12 h at room temperature. The resulting mixture was diluted with EtAc (15 ml). The organic layers were washed with H 2 and brine, dried over anhydrous Na 2 S 4 and the solvent was then removed under vacuo. The residue was purified with chromatography column on silica gel (gradient eluent of EtAc/petroleum ether: 1/100 to 1/50) to give the corresponding products 3 or 4 in yields listed in Table 2 and Table 3. Ar R 1 R S3

4 Characterization of Products 3 3a: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (m, 1H), (m, 7H), (ddd, J = 46.8, 8.4, 4.4 Hz, 1H), (ddd, J = 16.8, 14.8, 8.0 Hz, 1H), (ddd, J = 30.0, 17.2, 4.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), (d, J = 19.6 Hz), 136.7, 133.5, 128.7, 128.6, 128.2, (d, J = 6.6 Hz), 90.3 (d, J = Hz), 45.9 (d, J = 25.9 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.2, 30.1, 18.8 Hz, 1); IR (KBr): υmax 1686, 1449, 1205 cm -1 ; HRMS(ESI) calcd for C 15 H 13 Na [M+Na] , found b: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 8.4 Hz, 2H), (m, 5H), (m, 2H), (ddd, J = 46.4, 8.0, 4.0 Hz, 1H), (ddd, J = 17.2, 15.2, 8.4 Hz, 1H), (ddd, J = 30.2, 17.2, 4.4 Hz, 1H), 2.42 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 195.7, 144.4, (d, J = 19.6 Hz), 134.2, 129.4, 128.6, 128.3, (d, J = 6.8 Hz), 90.4 (d, J = Hz), 45.8 (d, J = 26.0 Hz), 21.7; 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 48.9, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1683, 1004 cm -1 ; HRMS(ESI) calcd for C 16 H 15 Na [M+Na] , found c: R f 0.3 (EtAc/petroleum ether = 1:20); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 2H), (m, 5H), (m, 2H), (ddd, J = 46.8, 8.4, 4.0 Hz, 1H), 3.90 (s, 3H), (ddd, J = 16.8, 14.8, 8.4 Hz, 1H), (ddd, J = 30.0, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), 163.8, (d, J = 19.6 Hz), 130.5, 129.8, 128.6, (d, J = 6.8 Hz), 113.8, 90.5 (d, J = S4

5 169.8 Hz), 55.5, 45.6 (d, J = 26.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1676, 1600, 1261, 1169 cm -1 ; HRMS(ESI) calcd for C 16 H 15 Na 2 [M+Na] , found d: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 2H), (m, 5H), (m, 2H), (ddd, J = 46.4, 8.0, 4.0 Hz, 1H), (ddd, J = 16.8, 14.8, 8.4 Hz, 1H), (ddd, J = 30.0, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), (d, J = Hz), (d, J = 19.6 Hz), 133.2, (d, J = 9.4 Hz), 128.7, 128.5, (d, J = 6.6 Hz), (d, J = 21.8 Hz), 90.3 (d, J = Hz), 45.9 (d, J = 26.2 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1), (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1687, 1597, 1206, 1156 cm -1 ; HRMS(ESI) calcd for C 15 H 12 2 Na [M+Na] , found Cl 3e: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 8.8 Hz, 2H), (m, 7H), (ddd, J = 46.8, 8.4, 4.0 Hz, 1H), (ddd, J = 16.8, 14.8, 8.4 Hz, 1H), (ddd, J = 30.2, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), 140.0, (d, J = 19.6 Hz), 135.0, 129.6, 129.0, 128.7, 128.6, (d, J = 6.6 Hz), 90.2 (d, J = Hz), 45.9 (d, J = 26.2 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1687, 1589, 911, 740 cm -1 ; HRMS(ESI) calcd for C 15 H 12 ClNa [M+Na] , found Br 3f: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ S5

6 (d, J = 8.8 Hz, 2H), (d, J = 8.8 Hz, 2H), (m, 5H), (ddd, J = 46.8, 8.4, 4.0 Hz, 1H), (ddd, J = 16.8, 14.4, 8.0 Hz, 1H), (ddd, J = 30.0, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), 145.4, (d, J = 19.6 Hz), 135.4, 132.0, 131.9, 129.7, 128.8, 128.7, (d, J = 6.6 Hz), 90.2 (d, J = Hz), 45.9 (d, J = 26.2 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1688, 1584, 1397, 1069, 1008 cm -1 ; HRMS(ESI) calcd for C 15 H 12 BrNa [M+Na] , found I 3g: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 8.4 Hz, 2H), (d, J = 8.4 Hz, 2H), (m, 5H), (ddd, J = 46.4, 8.4, 4.0 Hz, 1H), (ddd, J = 16.8, 14.8, 8.4 Hz, 1H), (ddd, J = 30.0, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 195.4, (d, J = 19.7 Hz), 138.0, 135.9, 129.6, 128.7, (d, J = 6.6 Hz), 101.7, 90.1 (d, J = Hz), 45.8 (d, J = 26.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1680, 1603, 1004 cm -1 ; HRMS(ESI) calcd for C 15 H 12 INa [M+Na] , found S 3h: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ 7.73 (d, J = 3.2 Hz, 1H), (d, J = 4.8 Hz, 1H), (m, 5H), (dd, J = 4.0, 4.4 Hz, 1H), (ddd, J = 46.8, 8.4, 4.0 Hz, 1H), (ddd, J = 23.2, 14.8, 4.8Hz, 1H), (ddd, J = 31.2, 16.4, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), 144.0, (d, J = 19.6 Hz), 134.5, 132.6, 128.7, 128.6, 128.2, (d, J = 6.6 Hz), 90.2 (d, J = Hz), 46.7 (d, J = 26.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1658, 1415, 1212 cm -1 ; HRMS(ESI) calcd for C 13 H 11 NaS [M+Na] , found S6

7 3i: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ 8.46 (s, 1H), (m, 4H), (m, 7H), (ddd, J = 46.4, 8.0, 4.0 Hz, 1H), (ddd, J = 16.8, 14.8, 8.4 Hz, 1H), (ddd, J = 30.0, 16.8, 4.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 196.0, (d, J = 19.5 Hz), 135.7, 134.0, 132.4, 130.1, 129.6, 128.7, 128.6, 127.8, 126.9, (d, J = 6.6 Hz), 123.7, 90.4 (d, J = Hz), 46.0 (d, J = 26.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1681, 1374, 1283, 1183 cm -1 ; HRMS(ESI) calcd for C 19 H 15 Na [M+Na] , found S7

8 Characterization of Products 4 4a: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (m, 1H), (m, 2H), (d, J = 7.6 Hz, 2H), (d, J = 8.0 Hz, 2H), (ddd, J = 46.4, 8.0, 4.0 Hz, 1H), (ddd, J = 16.8, 14.4, 8.0 Hz, 1H), (ddd, J = 29.2, 16.8, 4.0 Hz, 1H), 2.37 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 196.2, 138.5, 136.7, (d, J = 19.8 Hz), 133.4, 129.3, 128.7, 128.2, (d, J = 6.4 Hz), 90.3 (d, J = Hz), 45.8 (d, J = 26.4 Hz), 21.2; 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1687, 1598, 1208, 1014 cm -1 ; HRMS(ESI) calcd for C 16 H 15 Na [M+Na] , found Bu t 4b: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 8.4 Hz, 2H), (t, J = 7.6 Hz, 1H), (m, 6H), (ddd, J = 46.4, 8.0, 4.0 Hz, 1H), (ddd, J = 16.8, 14.4, 8.4 Hz, 1H), (ddd, J = 30.0, 17.2, 4.0 Hz, 1H), 1.33 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), 151.8, 136.7, (d, J = 19.5 Hz), 133.5, 128.7, 128.2, 125.6, (d, J = 6.4 Hz), 90.2 (d, J = Hz), 45.8 (d, J = 26.3 Hz), 34.6, 31.3; 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1688, 1445, 1207, 1017 cm -1 ; HRMS(ESI) calcd for C 19 H 21 Na [M+Na] , found Br 4c: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 2H), (m, 5H), (d, J = 8.0 Hz, 2H), (ddd, J = 46.4, S8

9 8.0, 4.8 Hz, 1H), (ddd, J = 17.2, 14.8, 8.0 Hz, 1H), (ddd, J = 27.6, 16.8, 4.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 195.8, (d, J = 20.0 Hz), 136.5, 133.6, 131.8, 129.8, 128.7, 128.5, 128.2, (d, J = 6.6 Hz), 122.6, 89.7 (d, J = Hz), 45.8 (d, J = 26.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1); IR (KBr): υmax 1685, 1208, 1008 cm -1 ; HRMS(ESI) calcd for C 15 H 12 BrNa [M+Na] , found d: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (m, 2H), (m, 3H), (m, 4H), (ddd, J = 46.8, 8.4, 4.0 Hz, 1H), (ddd, J = 17.2, 15.2, 8.4 Hz, 1H), (ddd, J = 30.4, 17.2, 4.0 Hz, 1H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 196.2, 139.3, 138.4, 136.7, 133.5, 129.4, 128.7, 128.5, 128.2, (d, J = 6.5 Hz), (d, J = 6.8 Hz), 90.3 (d, J = Hz), 45.9 (d, J = 26.1 Hz), 21.4; 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1688, 1370, 1001 cm -1 ; HRMS(ESI) calcd for C 16 H 15 Na [M+Na] , found Br 4e: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.2 Hz, 2H), (m, 2H), (m, 3H), (d, J = 7.6 Hz, 1H), (t, J = 7.6 Hz, 1H), (ddd, J = 46.0, 8.0, 4.4 Hz, 1H), (ddd, J = 17.2, 15.2, 8.0 Hz, 1H), (ddd, J = 28.8, 17.2, 4.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 3.6 Hz), (d, J = 19.9 Hz), 136.4, 133.7, 131.7, 130.2, 128.7, (d, J = 7.2 Hz), 128.2, (d, J = 6.6 Hz), 122.7, 89.4 (d, J = Hz), 45.8 (d, J = 25.7 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (ddd, J = 45.1, 30.1, 15.0 Hz, 1); IR (KBr): υmax 1686, 1207, 689 cm -1 ; HRMS(ESI) calcd for C 15 H 12 BrNa [M+Na] , found S9

10 Cl 4f: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.2 Hz, 2H), (d, J = 7.6 Hz, 2H), (m, 2H), (m, 3H), (ddd, J = 46.4, 9.2, 2.4 Hz, 1H), (m, 1H), (ddd, J = 31.6, 17.2, 2.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 195.5, (d, J = 21.1 Hz), 136.5, 133.5, (d, J = 5.6 Hz), 129.6, 129.5, 128.7, 128.2, 127.2, (d, J = 10.4 Hz), 87.3 (d, J = Hz), 44.5 (d, J = 25.0 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1); IR (KBr): υmax 1688, 1367, 1207, 1017 cm -1 ; HRMS(ESI) calcd for C 15 H 12 ClNa [M+Na] , found g: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (t, J = 7.6 Hz, 1H), (m, 4H), (m, 2H), (d, J = 7.6 Hz, 1H), (t, J = 14.8 Hz, 1H), (dd, J = 23.6, 14.8 Hz, 1H), (d, J = 23.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 4.9 Hz), (d, J = 21.8 Hz), 137.5, 133.2, 128.6, 128.5, 128.3, 127.7, (d, J = 9.1 Hz), 95.9 (d, J = Hz), 49.9 (d, J = 25.2 Hz), 26.7 (d, J = 24.2 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1); IR (KBr): υmax 1677, 1448, 1216 cm -1 ; HRMS(ESI) calcd for C 16 H 15 Na [M+Na] , found h: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (t, J = 7.6 Hz, 1H), (m, 2H), (d, J = 8.4 Hz, 2H), (d, J = 8.0 Hz, 2H), (t, J = 14.8 Hz, 1H), (dd, J = 23.2, 15.2 Hz, 1H), 2.34 (s, 3H), (d, J = 23.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 4.6 Hz), (d, J = 21.7 Hz), (d, J = 9.8 Hz), 133.1, 129.1, 129.0, 128.6, 128.4, 125.7, (d, J = 8.7 Hz), 96.0 (d, J = S10

11 Hz), 49.9 (d, J = 25.3 Hz), 26.7 (d, J = 24.1 Hz), 21.0; 19 NMR (376 MHz, CDCl 3 ): δ (m, 1); IR (KBr): υmax 1678, 1213, 1079, 1005 cm -1 ; HRMS(ESI) calcd for C 17 H 17 Na [M+Na] , found Cl 4i: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (t, J = 7.6 Hz, 1H), (t, J = 8.0 Hz, 2H), (m, 4H), (m, 2H), (d, J = 23.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 5.5 Hz), (d, J = 21.9 Hz), 137.2, 133.6, 133.3, 128.5, 128.4, (d, J = 9.2 Hz), 95.6 (d, J = Hz), 49.7 (d, J = 25.1 Hz), 26.8 (d, J = 24.1 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1); IR (KBr): υmax 1677, 1089, 1008, 746 cm -1 ; HRMS(ESI) calcd for C 16 H 14 ClNa [M+Na] , found j: R f 0.4 (EtAc/petroleum ether = 1:50); 1 H NMR (400 MHz, CDCl 3 ): δ (d, J = 7.6 Hz, 2H), (t, J = 7.6 Hz, 1H), (m, 4H), (t, J = 8.8 Hz, 2H), (m, 2H), (d, J = 23.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ (d, J = 5.9 Hz), (d, J = Hz), (d, J = 22.0 Hz), 137.3, 133.3, 128.5, 126.2, 126.1, (d, J = 21.3 Hz), 95.7 (d, J = Hz), 49.9 (d, J = 25.6 Hz), 26.8 (d, J = 23.9 Hz); 19 NMR (376 MHz, CDCl 3 ): δ (m, 1), (m, 1); IR (KBr): υmax 1679, 1511, 1219 cm -1 ; HRMS(ESI) calcd for C 16 H 14 2 Na [M+Na] , found S11

12 Investigation of the Reaction chanism Ph 1a + Ph 2a H standard conditions TEMP (1 equiv.) Ph Ph 3a, trace When the TEMP was added to the reaction of 1a and 2a with Selectfluor under the standard conditions, only trace amount of the desired product 3a was detected. The result indicates that the radical intermediate should be involved in the catalytic cycle of the reaction. standard + H conditions Ph Ph BHT (1 equiv.) Ph Ph 1a 2a 3a, 27% When the BHT was added to the reaction of 1a and 2a with Selectfluor under the standard conditions, the desired product 3a was only isolated in 27% yield. The result indicates that the radical intermediate should be involved in the catalytic cycle of the reaction. S12

13 Investigation of the Reaction chanism AgN 3 (20 mol%) + H K 2 S 2 8, K Ph Ph Na Ph 2 S 4 (1 equiv.) acetone/h 1a 2a 2 (1:1), rt 3a, 0% R ( When the reaction of 1a and 2a was conducted with AgN 3 (20 mol%), K 2 S 2 8 (2 equiv.), Na 2 S 4 (1 equiv.) and K (2 equiv.) in acetone/h 2 at room temperature for 12 h, no desired product 3a was detected, suggesting that a reaction pathway other than a common Ag(II) intermediate might also be involved. AgN 3 (20 mol%) + H K 2 S 2 8, Ag Ph Ph Na Ph 2 S 4 (1 equiv.) acetone/h 1a 2a 2 (1:1), rt 3a, 0% R (3) When the reaction of 1a and 2a was conducted with AgN 3 (20 mol%), K 2 S 2 8 (2 equiv.), Na 2 S 4 (1 equiv.) and Ag (2 equiv.) in acetone/h 2 at room temperature for 12 h, no desired product 3a was detected, suggesting that a reaction pathway other than a common Ag(II) intermediate might also be involved. S13

14 References (1) K. Wadhwa, C.Yang, P. R. West, K. C. Deming, S. R. Chemburkar and R. E. Reddy, Synth. Commun., 2008, 38, S14

15 1 H NMR and 13 C NMR Spectra of the Products 3 3a S15

16 3a 3a S16

17 S17

18 3b S18

19 3b S19

20 3c S20

21 3c S21

22 S22

23 3d 3d S23

24 3d S24

25 3e Cl 3e Cl S25

26 3e Cl S26

27 3f Br 3f Br S27

28 3f Br S28

29 3g I 3g I S29

30 3g I S30

31 3h S 3h S S31

32 3h S S32

33 3i S33

34 3i 3i S34

35 1 H NMR and 13 C NMR Spectra of the Products 4 4a 4a S35

36 4a S36

37 S37

38 Bu t 4b Bu t 4b S38

39 Bu t 4b S39

40 Br 4c Br 4c S40

41 Br 4c S41

42 4d 4d S42

43 4d S43

44 Br 4e S44

45 Br 4e Br 4e S45

46 S46

47 Cl 4f Cl 4f S47

48 Cl 4f S48

49 4g 4g S49

50 S50

51 4g S51

52 4h 4h S52

53 4h S53

54 Cl 4i Cl 4i S54

55 Cl 4i S55

56 4j 4j S56

57 4j S57