Electronic upplementary Material (E) for RC Advances. This journal is The Royal ociety of Chemistry 204 upplementary nformation Direct difunctionalization of alkynes with sulfinic acids and melecular iodine: a simple and convenient approach to (E)-βiodovinyl sulfones Wei Wei, Jiangwei Wen, Daoshan Yang, Huijun Jing, Jinmao You, Hua Wang a* a The Key Laboratory of Life-rganic Analysis and Key Laboratory of Pharmaceutical ntermediates and Analysis of Natural Medicine, chool of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 27365, handong, China. * Phone: +86 537 445837; Fax: +86 537 445837. E-mail: huawang_qfnu@26.com Contents. General information..............2 2. General procedure for direct synthesis of (E)-β-iodovinyl sulfones via difunctionalization of alkynes with sulfinic acids and melecular iodine...3 3. The procedure for the reaction of (E)-β-iodovinyl sulfones with alkyne leading to alkynylation products...... 3 4. The procedure for the synthesis for the synthesis of acetylenic sulfone (5aa)... 3 5. The procedure for the synthesis for the synthesis of (E)-vinyl sulfones... 4 6. Characterization data of products 3aa 6af.... 4-7. Reference.2 8. Copies of NMR spectra for 3aa 6af.....2-40 / 40
. General information All commercially available reagent grade chemicals were purchased from Aldrich, Acros, Alfa Aesar and Beijing uhe Chemical Company and used as received without further purification unless otherwise stated. All solvents were dried according to standard procedures. H NMR and 3 C NMR were recorded in CDCl 3 on a Bruker Avance 400 spectrometer with TM as internal standard (400 MHz H, 00 MHz 3 C) at room temperature, the chemical shifts (δ) were expressed in ppm and J values were given in Hz. The following abbreviations are used to indicate the multiplicity: singlet (s), doublet (d), triplet (t), quartet (q), doublet of doublets (dd), doublet of triplets (dt), and multiplet (m). All first order splitting patterns were assigned on the basis of the appearance of the multiplet. plitting patterns that could not be easily interpreted were designated as multiplet (m). Mass analyses and HRM were obtained on a Finnigan-LCQDECA mass spectrometer and a Bruker Daltonics Bio-TF-Q mass spectrometer by the E method, respectively. Column chromatography was performed on silica gel (200-300 mesh). 2 / 40
2. General procedure for direct synthesis of (E)-β-iodovinyl sulfones via difunctionalization of alkynes with sulfinic acids and melecular iodine. R R 2 + R3 H + 2 DME 00 o C R 2 R 3 R 2 n a sealed tube, alkynes (0.5 mmol), sulfinic acids (.0 mmol), molecular iodine (0.5 mmol), and DME (2 ml) were added. The mixture was allowed to stir at 00 o C for 2-24h. After the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired product. 3. The procedure (A) for the reaction of (E)-β-iodovinyl sulfone with alkynes leading to alkynylation products. Ar + R PdCl 2 (PPh 3 ) 2 (3mol%) Cu (5 mol%) Et 3 N, THF, h To a mixture of (E)-β-iodovinyl sulfone 3aa (0.25 mmol), PdCl 2 (PPh 3 ) 2 (3 mol%) Cu (5 mol%), Et 3 N (0.25 mmol), and alkyne (0.75 mmol) in a 25 ml roundbottomed flack at room temperature, was added the THF (2 ml). The reaction vessel was allowed to stir at room temperature for h. After the reaction, the solution was concentrated in vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired products. 4. The procedure (B) for the synthesis of acetylenic sulfone (5aa). 3 / 40
K 2 C 3 ( mmol) Ph H Ph + + 2 DME, 00 o C,2h Ph 2 Ph n a sealed tube, phenylacetylene a (0.5 mmol), benzenesulfinic acid 2a (.0 mmol), molecular iodine (0.5 mmol), K 2 C 3 ( mmol), and DME (2 ml) were added. The mixture was allowed to stir at 00 o C for 2h. After the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired product 5aa (78%). 5. The procedure (C) for the synthesis of (E)-vinyl sulfones. X + Y H 2 DCE, 60 o C X Y n a sealed tube, alkenes (0.5 mmol), sulfinic acids (.0 mmol), molecular iodine (0.5 mmol), and DCE (2 ml) were added. The mixture was allowed to stir at 60 o C for 2h. After the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired (E)-vinyl sulfones. 6. Characterization data of products 3aa-6af (E)-(-iodo-2-(phenylsulfonyl)vinyl)benzene [] Compound 3aa was obtained in 88% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.6-7.55 (m, 3H), 7.4 (s, H), 7.40 (t, J = 7.8 Hz, 2H), 7.34-7.28 (m, 3H), 7.25-7.23 (m, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4., 40.3, 39.6, 33.5, 29.8, 29.0, 28.0, 27.8, 27.7, 4.7; HRM calc. for C 4 H 2 Na (M+Na) +, 392.9422; found, 392.9424. (E)--(-iodo-2-(phenylsulfonyl)vinyl)-4-methoxybenzene [] 4 / 40 Me
Compound 3ba was obtained in 88% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.63 (d, J = 7.3 Hz, 2H), 7.56 (d, J = 7.4 Hz, H), 7.42 (t, J = 7.9 Hz, 2H), 7.33 (s, H), 7.27 (t, J = 6.6 Hz, 2H), 6.8 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 60.9, 40.5, 40.2, 33.5, 3.8, 30.0, 29.0, 27.8, 5.5, 3.3, 55.4; HRM calc. for C 5 H 3 3 Na (M+Na) +, 422.9528; found, 422.9529. (E)--(-iodo-2-(phenylsulfonyl)vinyl)-4-methylbenzene [] Compound 3ca was obtained in 75% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.64-7.62 (m, 2H), 7.57 (t, J = 7.5 Hz, H), 7.4 (t, J = 8. Hz, 2H), 7.37 (s, H), 7.7 (d, J = 8.2 Hz, 2H), 7.0 (d, J = 8.0 Hz, 2H), 2.37 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 40.6, 40.4, 40.3, 36.8, 33.5, 29.0, 28.6, 27.8, 5.4, 2.5; HRM calc. for C 5 H 3 2 Na (M+Na) +, 406.9579; found, 406.9577. (E)--(-iodo-2-(phenylsulfonyl)vinyl)-3-methylbenzene Compound 3da was obtained in 90% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.59-7.53 (m, 3H), 7.4 (s, H), 7.39 (t, J = 8.3 Hz, 2H), 7.8 (t, J = 7.6 Hz, H), 7. (d, J = 7.6 Hz, H), 7.05 (d, J = 7.5 Hz, H), 6.93 (s, H), 2.28 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4., 40.3, 39.5, 37.7, 33.4, 30.7, 28.9, 28.0, 27.9, 27.9, 24.8, 5.2, 2.3; HRM calc. for C 5 H 4 2 (M+H) +, 384.9759; found, 384.9759. (E)--fluoro-4-(-iodo-2-(phenylsulfonyl)vinyl)benzene [] F Compound 3ea was obtained in 7% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.64-7.58 (m, 3H), 7.45 (t, J = 8. Hz, 2H), 7.40 (s, H), 7.28-7.25 (m, 2H), 6.99 (d, J = 8.6 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 63.2 (d, J = 250. Hz), 4.5, 40.2, 35.6 (d, J = 4. Hz), 33.7, 30.0 (d, J = 34.6 Hz), 29., 27.8, 5. (d, J = 22.0 Hz), 3.; HRM calc. for C 4 H 0 F 2 Na (M+Na) +, 40.9328; found, 40.9324. 5 / 40
(E)--chloro-4-(-iodo-2-(phenylsulfonyl)vinyl)benzene [] Compound 3fa was obtained in 73% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.65-7.59 (m, 3H), 7.45 (t, J = 8.0 Hz, 2H), 7.39 (s, H), 7.28 (d, J = 8.6 Hz, 2H), 7.9 (d, J = 8.5 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.6, 40., 38.0, 36.0, 33.7, 29.2, 29., 28.3, 27.8, 2.7; HRM calc. for C 4 H 0 Cl 2 Na (M+Na) +, 426.9032; found, 426.9033. (E)--bromo-4-(-iodo-2-(phenylsulfonyl)vinyl)benzene [] Cl Br Compound 3ga was obtained in 83% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.65-7.60 (m, 3H), 7.48-7.43 (m, 4H), 7.40 (s, H), 7.2 (d, J = 8.5 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.6, 40., 38.5, 33.7, 3.2, 29.3, 29.2, 27.8, 24.3, 2.6; HRM calc. for C 4 H 0 Br 2 Na (M+Na) +, 470.8527; found, 470.8529. (E)-4-(-iodo-2-(phenylsulfonyl)vinyl)benzonitrile NC Compound 3ha was obtained in 78% yield according to the general procedure (6h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.67-7.62 (m, 5H), 7.50 (t, J = 7.4 Hz, 2H), 7.4 (s, H), 7.36 (d, J = 8.5 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 44., 42., 39.9, 34., 3.8, 29.4, 28.2, 27.8, 8.0, 3.4, 0.4; HRM calc. for C 5 H 0 N 2 Na (M+Na) +, 47.9375; found, 47.9370. (E)-4-(-iodo-2-(phenylsulfonyl)vinyl)biphenyl Ph Compound 3ia was obtained in 90% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.65-7.59 (m, 4H), 7.57 (t, J = 7.5 Hz, H), 7.52-7.48 (m, 4H), 7.45 (s, H), 7.44-7.38 (m, 3H), 7.32 (d, J = 8.3 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 42.7, 4.3, 40.3, 40.0, 38.4, 33.5, 29.0, 28.9, 28.4, 28.0, 27.9, 27., 26.6, 4.4; HRM calc. for C 20 H 5 2 Na (M+Na) +, 468.9735; found, 468.9729. 6 / 40
(E)-3-(-iodo-2-(phenylsulfonyl)vinyl)thiophene Compound 3ja was obtained in 62% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.66-7.63 (m, 2H), 7.60 (dd, J =.3 Hz, J 2 = 3.0 Hz, H), 7.56 (t, J = 7.5 Hz, H), 7.42 (t, J = 8. Hz, 2H), 7.39 (s, H), 7.2 (dd, J = 3.0 Hz, J 2 = 5.0 Hz, H), 6.95 (dd, J =.3 Hz, J 2 = 5.0 Hz, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.3, 40.2, 38.8, 33.5, 29.0, 28.4, 27.6, 25.5, 08.0; HRM calc. for C 2 H 9 2 2 Na (M+Na) +, 398.8986; found, 398.8983. (E)-(-iodo--phenylprop--en-2-ylsulfonyl)benzene 7 / 40 Me Compound 3ka was obtained in 70% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.53-7.50 (m, 3H), 7.37 (t, J = 6.5 Hz, 2H), 7.25-7.22 (m, 3H), 7.2-7.0 (m, 2H), 2.56 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 44.0, 42.8, 40.4, 33., 28.9, 28.7, 27.7, 27.7, 27.6, 6., 27.0; HRM calc. for C 5 H 4 2 (M+H) +, 384.9759; found, 384.9757. (E)--(-iodo-2-(phenylsulfonyl)prop--enyl)naphthalene Compound 3la was obtained in 82% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.86-7.80 (m, 2H), 7.7 (s, H), 7.54 (d, J = 8. Hz, H), 7.47-7.38 (m, 4H), 7.32 (d, J = 7.3 Hz, 2H), 7.24 (t, J = 7.4 Hz, H), 7.06 (t, J = 8.0 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 43.7, 39.2, 36., 33.4, 33., 30.2, 28.5, 28.3, 27.8, 26.6, 26.3, 25.2, 25.0, 24.9, 2.4; HRM calc. for C 8 H 3 2 Na (M+Na) +, 442.9579; found, 442.9578. (E)-ethyl 2-iodo-3-(phenylsulfonyl)acrylate Et Compound 3ma was obtained in 36% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 8.00-7.98 (m, 2H), 7.7 (t, J = 7.4 Hz, H), 7.60 (t, J = 8.0 Hz, 2H), 6.98 (s, H), 4.45 (q, J = 7.2 Hz, 2H),.43 (t, J = 7. Hz, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 64.6, 39.7, 39.0, 34.3, 29.6, 28.2, 00.4, 63.4, 3.8; HRM calc. for C H 4 Na (M+Na) +, 388.9320; found, 388.939.
(E)-(2-iodohex--enylsulfonyl)benzene [] Compound 3na was obtained in 2% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.95-7.92 (m, 2H), 7.69 (t, J = 7.4 Hz, H), 7.60 (t, J = 7.9 Hz, 2H), 7.04 (s, H), 3.06 (t, J = 7.4 Hz, 2H),.56-.5 (m, 2H),.42-.37 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.0, 38.6, 33.7, 29.5, 27.5, 26.2, 39.9, 32.0, 2.7, 3.8; HRM calc. for C 2 H 5 2 Na (M+Na) +, 372.9735; found, 372.9733. (E)--(2-iodo-2-phenylvinylsulfonyl)-4-methylbenzene [] Compound 3ab was obtained in 88% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.48 (d, J = 8.3 Hz, 2H), 7.38 (s, H), 7.34-7.28 (m, 3H), 7.26-7.24 (m, 2H), 7.2 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 44.6, 4.3, 39.7, 37.4, 29.8, 29.7, 27.9, 27.9, 27.7, 4.2, 2.6; HRM calc. for C 5 H 3 2 Na (M+Na) +, 406.9579; found, 406.9577. (E)--(2-iodo-2-p-tolylvinylsulfonyl)-4-methylbenzene [2] Compound 3bb was obtained in 74% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.52 (d, J = 8.3 Hz, 2H), 7.33 (s, H), 7.24-7.8 (m, 4H), 7.2 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H), 2.38 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 44.5, 40.7, 40.2, 37.5, 36.9, 29.7, 28.6, 27.9, 27.8, 4.8, 2.6, 2.5; HRM calc. for C 6 H 5 2 Na (M+Na) +, 420.9735; found, 420.9736. (E)--chloro-4-(2-iodo-2-phenylvinylsulfonyl)benzene 8 / 40 Cl Compound 3ac was obtained in 8% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.48 (d, J = 8.7 Hz, 2H), 7.4 (s, H), 7.37-7.28 (m, 5H), 7.22-7.20 (m, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.0, 40.2, 39.5, 38.7, 30.0, 29.3, 29.3, 28., 27.7, 5.3; HRM calc. for C 4 H 0 Cl 2 Na (M+Na) +, 426.9032; found, 426.9037.
(E)--chloro-4-(2-iodo-2-p-tolylvinylsulfonyl)benzene Compound 3bc was obtained in 70% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.5 (d, J = 8.3Hz, 2H), 7.37 (s, H), 7.29-7.24 (m, 4H), 7.00 (t, J =8.6 Hz, 2H), 2.43 (s, 3H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 64.5, 62.0, 44.8, 4.7, 37.3, 35.7, 30., 30.0, 29.8, 27.8, 5.2, 5.0, 2.6, 2.6; HRM calc. for C 5 H 2 Cl 2 Na (M+Na) +, 440.989; found, 440.987. (E)--(2-iodo-2-phenylvinylsulfonyl)-4-(trifluoromethyl)benzene Cl CF 3 Compound 3ad was obtained in 77% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.69-7.62 (m, 4H), 7.45 (s, H), 7.34 (t, J = 7.3 Hz, H), 7.30-7.26 (m, 2H), 7.8 (d, J = 7. Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 43.7, 40.7, 39.4, 35.0 (d, J = 32.9 Hz), 30., 28.4, 28., 27.6, 26.0 (q, J = 3.6 Hz), 23.0 (q, J = 256. Hz), 6.0; HRM calc. for C 5 H 0 F 3 2 Na (M+Na) +, 460.9296; found, 460.9299. CF 3 (E)--(2-iodo-2-phenylvinylsulfonyl)-2-(trifluoromethyl)benzene Compound 3ae was obtained in 86% yield according to the general procedure (6h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.82 (d, J = 7.8 Hz, H), 7.64 (t, J = 7.6 Hz, H), 7.57 (d, J = 7.9 Hz, H), 7.5 (d, J =.4 Hz, H), 7.40 (t, J = 7.4 Hz, H), 7.28 (t, J = 7.2 Hz, H), 7.22 (t, J = 7.6 Hz, 2H), 7.6-7.4 (m, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.7 (q, J = 22.4 Hz), 39.5, 38.7, 33.5, 32.0, 32.0, 29.8, 28.5 (d, J = 33.3 Hz), 28.2 (q, J = 6.0 Hz), 28.0, 27.5, 22.6 (q, J = 272.7 Hz), 4.5; HRM calc. for C 5 H 0 F 3 2 Na (M+Na) +, 460.9296; found, 460.9297. Br (E)--bromo-2-(2-iodo-2-phenylvinylsulfonyl)benzene Compound 3af was obtained in 87% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.65 (dd, J =. Hz, J 2 = 8.0 Hz, H), 7.62 (s, H), 7.48 (dd, J =.6 Hz, J 2 = 7.9 Hz, H), 7.32-7.28 (m, H), 7.20-7.7 (m, H), 9 / 40
7.5-7.0 (m, 5H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 40.4, 39.8, 39.3, 34.9, 34.2, 3.2, 29.8, 27.8, 27.4, 27.4, 20.6, 4.7; HRM calc. for C 4 H 0 Br 2 Na (M+Na) +, 470.8527; found, 470.8529. (E)-2-(2-iodo-2-phenylvinylsulfonyl)naphthalene Compound 3ag was obtained in 74% yield according to the general procedure (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 8.03 (d, J =.5 Hz, H), 7.89 (t, J = 8.8 Hz, 2H), 7.8 (t, J = 8. Hz, H), 7.69-7.58 (m, 3H), 7.49 (s, H), 7.26-7.23 (m, H), 7.2(d, J = 4.3 Hz, 4H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.3, 39.5, 36.9, 35., 32.0, 30.0, 29.9, 29.4, 29.3, 27.9, 27.7, 27.6, 22.4, 4.8; HRM calc. for C 8 H 3 2 Na (M+Na) +, 442.9579; found, 442.9578. Ph (E)-(4-(phenylsulfonyl)but-3-en--yne-,3-diyl)dibenzene Compound 4aa was obtained in 92% yield according to the procedure A (h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.70-7.67 (m, 2H), 7.54 (t, J = 7.5 Hz, H), 7.49-7.43 (m, 5H), 7.42-7.34 (m, 7H), 7.00 (s, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.0, 37.4, 35.3, 34.2, 33.3, 32.0, 29.7, 29.6, 29., 28.9, 28.5, 28.0, 27.8, 2.6, 97.7, 88.3; HRM calc. for C 22 H 7 2 (M+H) +, 345.0949; found, 345.0943. Cl (E)--chloro-4-(3-phenyl-4-(phenylsulfonyl)but-3-en--ynyl)benzene Compound 4af was obtained in 84% yield according to the procedure A (h). H NMR (CDCl 3, 400 MHz, ppm): δ 7.69-7.67 (m, 2H), 7.55 (t, J = 7.5 Hz, H), 7.47-7.45 (m, 3H), 7.43-7.36 (m, 6H), 7.35-7.3 (m, 2H), 6.99 (s, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 40.8, 37.0, 35.9, 35.7, 34.0, 33.3, 33.2, 29.7, 29.0, 28.9, 28.9, 28., 27.8, 20.0, 96.3, 89.; HRM calc. for C 22 H 5 Cl 2 Na (M+Na) +, 40.0379; found, 40.0383. (phenylethynylsulfonyl)benzene 5aa [3] 0 / 40
Compound 5aa was obtained in 78% yield according to the procedure B (2h). H NMR (CDCl 3, 400 MHz, ppm): δ 8.2-8.0 (m, 2H), 7.72 (t, J = 7.4 Hz, H), 7.65-7.6 (t, J = 7.9 Hz, 2H), 7.56-7.54 (m, 2H), 7.49 (t, J = 7.6 Hz, H), 7.39 (t, J = 7.7 Hz, 2H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.8, 34.2, 32.8, 3.6, 29.4, 28.7, 27.4, 7.9, 93.5, 85.4; HRM calc. for C 4 H 0 2 Na (M+Na) +, 265.0299; found, 265.0293. (E)--fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (6ea) [4] F Compound 6ea was obtained in 73% yield according to the procedure C. H NMR (CDCl 3, 400 MHz, ppm): δ 7.97 (d, J = 7.7 Hz, 2H), 7.69-7.63 (m, 2H), 7.57 (t, J = 7.9 Hz, 2H), 7.52-7.49 (m, 2H), 7.0 (t, J = 8.5 Hz, 2H), 6.82 (d, J = 5.4 Hz, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 65.6 (d, J = 25.5Hz), 4.2, 40.7, 33.5, 30.6 (d, J = 8.7 Hz), 29.4, 28.7, 27.7, 27. (d, J = 2.4 Hz), 6.3 (d, J = 22.0 Hz); HRM calc. for C 4 H F 2 Na (M+Na) +, 285.036; found, 285.0366. (E)--chloro-4-(2-(phenylsulfonyl)vinyl)benzene (6fa) [4] Cl Compound 6fa was obtained in 74% yield according to the procedure C. H NMR (CDCl 3, 400 MHz, ppm): δ 7.97 (d, J = 7.2 Hz, 2H), 7.68-7.63 (m, 2H), 7.57 (t, J = 7.8 Hz, 2H), 7.45-7.37 (m, 4H), 6.87 (d, J = 5.4 Hz, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 4.0, 40.5, 37.3, 33.5, 30.9, 29.8, 29.4, 29,4, 28.0, 27.7; HRM calc. for C 4 H Cl 2 Na (M+Na) +, 30.0066; found, 30.0065. (E)--bromo-2-(styrylsulfonyl)benzene (6af) Br Compound 6af was obtained in 77% yield according to the procedure C. H NMR (CDCl 3, 400 MHz, ppm): δ 8.28 (dd, J =.7 Hz, J 2 = 7.9 Hz, H), 7.8 (d, J = 5.4 Hz, H), 7.7 (d, J =. Hz, J 2 = 7.9 Hz, H), 7.55-7.53 (m, 3H), 7.49-7.43 (m, 4H), 7.4 (d, J = 5.4 Hz, H); 3 C NMR (CDCl 3, 00 MHz, ppm): δ 45.5, 39.9, 35.5, 34.5, 32.4, 3.5, 3., 29.2, 28.7, 28., 25.0, 2.0; HRM calc. for C 4 H 2 BrNa (M+Na) +, 344.956; found, 344.9563. / 40
7. Reference [] X. Q. Li, X.. Xu and X. H. hi, Tetrahedron Lett; 203, 54, 307. [2] V. Nair, A. Augustine and T. D. uja, ynthesis, 2002, 2259. [3] H. Qian and X. Huang, Tetrahedron Lett 2002, 43, 059. [4] (a) M. Bian, F. Xu and C. Ma, ynthesis, 2007, 295. (b) A. Battace, T. Zair, H. Doucet and M. antelli, ynthesis, 2006, 3495. 2 / 40
8. Copies of NMR pectra for 3aa-6af. 3 / 40
Me Me 4 / 40
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F F 7 / 40
Cl Cl 8 / 40
Br Br 9 / 40
Ph Ph 20 / 40
NC NC 2 / 40
Me Me 22 / 40
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Et Et 25 / 40
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Cl Cl 29 / 40
Cl Cl 30 / 40
CF 3 CF 3 3 / 40
CF 3 CF 3 32 / 40
Br Br 33 / 40
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Ph Ph 35 / 40
Cl Cl 36 / 40
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F F 38 / 40
Cl Cl 39 / 40
Br Br 40 / 40