BINOL. Vol. 41 No Journal of Jiangxi Normal University Natural Science Sep C C

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1 41 5 Vol. 41 No Journal of Jiangxi Normal University Natural Science Sep BINOL α-ewg * BINOL α-ewg. BINOL 15% α-ewg α-ewg. BINOL O 626 A DOI /j. cnki. issn α-. C C 1. RH R' OH BINOL RH R'OH α-ewg α- X-6 α- Unity-400MHz TMS Zhang Qian CDCl 3 Bruker BF 3 Et 2 O BINOL α -EWG BINOL α- CuCl OH TMEDA NaOH 2 mol L ml h α- HCl 2 mol L - 1 ph 1 2 2'- -1 1'- -3 3' J czm000219@ 163. com

2 H NMR 13 C NMR BINOL ml 4C C C C g 50 mmol 50 ml C 2 H 5 OH 3 NaBH g 15 mmol. 60 min TLC 400 MHz CDCl 3 δ d J = 4. 0 Hz 4H ml s 1H d J =16. 0 Hz 1H d J = 8. 0 Hz. 2H d J = 8. 0 Hz 2H ~ m 99%. 10H d J = Hz 1H. 13 C NMR 4-98%. 100 MHz CDCl 3 δ BINOL α-ewg C C C a 2a 4C C ml 1a g 2C mmol 2a g mmol BINOL g mmol 2 ml DMSO. 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 5 h TLC 4H s 1H d J = Hz 1H ml d J = 4. 0 Hz 2H ~ m 9H d 10 ml 3 8 ml J = 8. 0 Hz 2H d J = Hz 1H. 13 C NMR 1 g 100 MHz CDCl 3 δ v C C v = 7 1 3a g 90%. 3b ~ 3t a m. p. 152 ~ H NMR 400 MHz CDCl 3 δ d J = 8. 0 Hz 4H s 1H d J = Hz 1H s 2H ~ m 13H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C b m. p. 79 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 1H d J = Hz 1H s 6H ~ m 8H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C c m. p. 151 ~ H NMR 3d m. p. 156 ~ H NMR 2C C C C e m. p. 161 ~ H NMR 400 MHz CDCl 3 δ d J = 8. 0 Hz 4H s 1H d J = Hz 1H d J = 4. 0 Hz 1H s 1H ~ m 1H ~ m 11H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C f m. p. 130 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = Hz 4H s 1H d J = Hz 1H d J = 8. 0 Hz 1H s 1H s 5H d J = Hz 6H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ 21. 1

3 5 BINOL α-ewg C C C C C BINOL α-ewg

4 g m. p. 118 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 4. 0 Hz 4H s 1H d J = Hz 1H s 4H ~ m 10H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C h m. p. 147 ~ H NMR 400 MHz CDCl 3 δ d J = 8. 0 Hz 6H d J =8. 0 Hz 4H s 1H d J = Hz 1H s 4H s 4H ~ m 5H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ ~ m 2H ~ m 12H. 13 C C C C NMR 100 MHz CDCl 3 δ C C i m. p. 144 ~ H NMR 400 MHz CDCl 3 δ d J = 4. 0 Hz 4H s 3H s 1H d J = Hz 1H d J = 8. 0 Hz 2H d J = 8. 0 Hz 2H 8. 0 Hz 4H s 1 H d J = Hz ~ m 10H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C j m. p. 136 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 3H s 1H d J = Hz 1H d J = 8. 0 Hz 2H ~ m 6H ~ m 5H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C k m. p. 114 ~ H NMR 400 MHz CDCl 3 δ d J = 4. 0 Hz 4H s 1H d J = Hz 1H d J = 8. 0 Hz 2H s 2H ~ m 10H d J = Hz 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C l m. p. 170 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 1H d J = Hz 1H d J = Hz 2H s 4H ~ m 7H s 1H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C m m. p. 204 ~ H NMR 400 MHz CDCl 3 δ d J = 4. 0 Hz 4H s 1H d J = Hz 1H s 1H C C C n m. p. 120 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 1H ~ m 7H d J = 8. 0 Hz 3H d J = Hz 4H. 13 C NMR 100 MHz CDCl 3 δ C C C C o m. p. 194 ~ H NMR 400 MHz CDCl 3 δ d J = 8. 0 Hz 4H s 1H d J = Hz 1H ~ m 12H d J = Hz 1H d J = 8. 0 Hz 2H. 13 C NMR 100 MHz CDCl 3 δ C C C C C p m. p. 161 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 1H d J = Hz 1H ~ m 11H d J = Hz 1H d J = 8. 0 Hz 2H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C

5 5 BINOL α-ewg q m. p. 217 ~ H NMR 400 MHz CDCl 3 δ d J = 8. 0 Hz 4H s 1H d J = Hz 1H ~ m 13H s 1H s 1H. 13 C NMR 100 MHz CDCl 3 δ C C C r m. p. 191 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 1H d J = Hz 1H ~ m 7H ~ m 5H s 1H s 1H. 13 C NMR 100 MHz CDCl 3 δ C C C s m. p. 141 ~ H NMR 400 MHz CDCl 3 δ d J = 4. 0 Hz 4H s 1H ~ m 2H s 8H d J = 7. 7 Hz 2H d J = 7. 3 Hz 1H d J = 8. 0 Hz 2H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C C t m. p. 112 ~ H NMR 400 MHz CDCl 3 δ s 3H d J = 8. 0 Hz 4H s 1H d J = 8. 0 Hz 2H ~ m 9H d J = 8. 0 Hz 1H d J = 7. 5 Hz 2H. 13 C NMR 100 MHz CDCl 3 δ C C C C C C a 0. 5 mmol 2a 0. 8 mmol 5 h a 2. 2 No. 1 ~ No. 4 3a 3a No. 2 90%. BINOL. No. 5 ~ No. 8 3a 3a 0. BINOL.. 3a 2. 2 a 3a No. Solvent 2 ml Cat 15 % t /h Yield /% 1 DMSO Naphthol acid DMSO BINOL acid DMSO Salicylic acid DMSO p-toluenesulfonic acid CH 2 Cl 2 BINOL acid 20-6 CH 3 CN BINOL acid 20-7 H 2 O BINOL acid BINOL acid 20 - a 1a 0. 5 mmol 2a 0. 8 mmol reflux 5 h a DMSO 2 ml 5 h 3a No. 1 ~ 5 h BINOL 3a 3. No. 4 BINOL 1% 5 h 3a 20% No. 5 BINOL BINOL 20% 5% 5 h 3a 7% No. 6.

6 α-ewg 1 2 α- EWG 3a ~ 3t 1. 3 a 3a /% /% a 1a 0. 5 mmol 2a 0. 8 mmol reflux 5 h alkenoyl ketene dithioacetals and analogues J. Synlett Junjappa H Ila H Asokan C V. α-oxoketene-s S- N S- 3 and N N-acetals Versatile intermediates in organic synthesis J. Tetrahedron ized 4H-chromenes and dihydrocoumarins based on copper 1 March Jerry. Advanced organic chemistry J. Advanced II bromide-catalyzed C-C coupling of benzylic alcohols Organic Chemistry with ketene dithioacetals J. Advanced Synthesis & Ca- 2 Zhang Qian Sun Shaoguang Hu Jianglei et al. BF 3 Et 2 O- talysis catalyzed direct carbon-carbon bond formation of α-ewg 14 Dong Ying Wang Mang Liu Jun. Cheminform abstract ketene- S S -acetals and alcohols and synthesis of unsymmetrical biaryls J. European Journal of Organic tion of ketene dithioacetals / vinylogous thioesters and aryl- aerobic Cu-catalyzed desulfitative C-C bond-forming reac- Chemistry boronic acids J. Chemical Communications CuBr 2 BF OEt J. J Guillena Gabriela Ramón Diego J Yus Miguel. Alcohols as electrophiles in C-C bond-forming reactions the hydrogen autotransfer process J. ChemInform BINOL 15% BINOL α-ewg 5 Yasuda Makoto Somyo Toshio Baba Akio. Direct carboncarbon bond formation from alcohols and active methylenes alkoxyketones or indoles catalyzed by indium trichloride J. Chem Inform Motokura Ken Fujita Noriaki Mori Kohsuke et al. Br nsted acid mediated heterogeneous addition reaction of 1 3-dicarbonyl compounds to alkenes and alcohols J. Angewandte Chemie International Edition Trost Barry M Quancard Jean. Palladium-catalyzed enantioselective C-3 allylation of 3-substituted-1H-indoles using trialkylboranes J. ChemInform Pan Ling Liu Qun Annulation strategy based on 10 Dieter R Karl. α-oxo ketene dithioacetals and related compounds versatile three-carbon synthons J. Tetrahedron α-ewg 1 2 BINOL DMSO α-ewg 3a ~ 11 Wang Mang Sun Shaoguang Liang Deqiang et al. Sulfuric 3t. acid-catalyzed regioselective alkylation of indoles and β- 3a naphthols with ketene dithioacetal-based allylic alcohols 3a. J. European Journal of Organic Chemistry a 0. 5 mmol 2a 0. 8 mmol % DMSO 2 ml 5 h 3a 12 Bi Xihe Dong Dewen Liu Qun et al Annulation 90%. a synthetic strategy for highly substituted phenols and cyclohexenones J. Journal of the American Chemical Society Liang Deqiang Wang Mang Bekturhun Bahargul et al. ChemInform abstract one-pot synthesis of polyfunctional- 16. / J

7 5 BINOL α-ewg 501 J Pellissier Hélène. Asymmetric organocatalysis J. Tetrahedron Dondoni Alessandro Massi Alessandro. Asymmetric organocatalysis From infancy to adolescence J. Angewandte Chemie International Edition Yu Haifeng Liao Peiqiu. Iron chloride hexahydrate-catalyzed Friedel-Crafts akylation of cyclic ketene dithioacetals with alcohols J. Chemical Research in Chinese Universities Noji M Nakajima M Koga K. A new catalytic system for aerobic oxidative coupling of 2-naphthol derivatives by the use of CuCl-amine complex A practical synthesis of binaphthol derivatives J. Tetrahedron Letters Cram Donald J Helgeson Roger C Peacock Stephen C et al. Host-guest complexation 8 Macrocyclic polyethers by two rigid substituted dinaphthyl or ditetraryl units J. European Journal of Organic Chemistry Yin Yanbing Wang Mang Liu Qun et al. A C-C bond formation reaction at the α-carbon atom of α-oxo ketene dithioacetals via the Baylis-Hillman type reaction J. Tetrahedron Letters Zhang Qian Liu Yun Wang Mang et al. Highly efficient C-C bond-forming reactions of an α -cyanoketene dithioacetal with aldehydes and ketones J. Cheminform Yuan Hongjuan Wang Mang Liu Yingjie et al. Copper Ⅱ catalyzed C-C bond-forming reactions of α-electron-withdrawing group-substituted ketene S S-acetals with carbonyl compounds and a facile synthesis of coumarins J. Advanced Synthesis & Catalysis Liu Yingjie Wang Mang Yuan Hongjuan et al. Copper II bromide / boron trifluoride etherate-cocatalyzed cyclization of ketene dithioacetals and p-quinones a mild and general approach to polyfunctionalized benzofurans J. Advanced Synthesis & Catalysis The BINOL Acid-Mediated Coupling Reaction of α -EWG Ketene Dithioacetals with Diphenylmethanol WANG Jinjuan WANG Wenchen YANG Zhixiang CHEN Zhiming * Key Laboratory of Functional Materials Chemistry of Guizhou Province College of Chemistry and Materials Science Guizhou Normal University Guiyang Guizhou China Abstract An inexpensive and environmentally friendly BINOL acid-mediated coupling reaction of α-ewg ketene dithioacetals with diphenylmethanol has been developed. The reaction is efficiently performed in the presence of BI- NOL acid 15 mmol% at reflux in DMSO forming α-ewg ketene dithioacetals derivatives in good yields. Key words BINOL acid diphenylmethanol ketene dithioacetals coupling reaction