Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (7): 815-819.DOI: 10.6023/A14060436 Previous Articles     Next Articles

Special Issue: 不对称催化与合成



于月娜, 徐明华   

  1. 中国科学院上海药物研究所 上海 201203
  • 投稿日期:2014-06-04 发布日期:2014-06-26
  • 通讯作者: 徐明华
  • 基金资助:


Chiral Phosphite-Olefin Ligands:Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to β-Aryl-α,β-unsaturated Sulfonates

Yu Yue-Na, Xu Ming-Hua   

  1. Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203
  • Received:2014-06-04 Published:2014-06-26
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21325209), the Shanghai Municipal Committee of Science and Technology (No. 14XD1404400).

Chiral sulfonyl compounds have great versatility in organic synthesis, and they are also important as biologically active substances in medicinal chemistry. Among various methods developed for their synthesis, rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated sulfonyl compounds represents one of the most practical methods due to the stability and availability of the boronic acid used as a nucleophile. Although several Rh(I) complexes of bidentate ligands have been discovered for asymmetric conjugation addition of α,β-unsaturated sulfonyl compounds, some challenging issues still remain in terms of efficiency, enantioselectivity and substrate scope. Therefore, the development of an efficient catalytic system for the synthesis of chiral sulfonyl compounds is an important goal in extending the current methodology. Here, a general and mild method for the rhodium-catalyzed enantioselective catalytic conjugate addition of arylboronic acids to β-aryl-α,β-unsaturated sulfonate is described. The success of the process relies on the use of extraordinary simple chiral phosphite-olefin ligands as bidentate ligands which offer notable synthetic and economic advantages. Optimum reaction condition was determined to run the reaction at 50 ℃ using dioxane as the solvent, in the presence of 2.5 mol% of [Rh(coe)2Cl]2 and 5 mol% of chiral P/olefin ligand L7. This Rh(I) catalyst containing chiral P/olefin ligand has a broad substrate scope, a wide range of arylboronic acids with varying electronic and steric demands were successfully examined with α,β-unsaturated sulfonate (1). Notably, all transformations proceed efficiently to give the desired products in good yields (84%~95%) and excellent selectivities (92%~99% ee). The electronic properties of the arylboronic acids did not appear to affect the reactivity of the reaction. Besides, α,β-unsaturated sulfonate 1 with either an electron-donating or electron-withdrawing group on any aromatic carbon readily underwent the asymmetric arylation with arylboronic acids, affording chiral sulfonates in high yields and enantioselectivities. The current reaction provides a practical approach to the synthesis of diverse highly enantioenriched gem-diaryl substituted sulfonates.

Key words: asymmetric catalysis, P/olefin ligand, α,β-unsaturated sulfonate, 1,4-addition, chiral gem-diaryl compound