Chiral Phosphite-Olefin Ligands: Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to beta-Aryl-alpha,beta-unsaturated Sulfonates
文献类型：期刊论文
| 作者 | Yu Yue-Na; Xu Ming-Hua
|
| 刊名 | ACTA CHIMICA SINICA
 |
| 出版日期 | 2014-07-15 |
| 卷号 | 72期号:7页码:815-819 |
| 关键词 | asymmetric catalysis P/olefin ligand alpha,beta-unsaturated sulfonate 1,4-addition chiral gem-diaryl compound |
| ISSN号 | 0567-7351 |
| DOI | 10.6023/A14060436 |
| 文献子类 | Article |
| 英文摘要 | 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 alpha,beta-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 alpha,beta-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 beta-aryl-alpha,beta-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 degrees C using dioxane as the solvent, in the presence of 2.5 mol% of [Rh(coe)(2)Cl](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 alpha,beta-unsaturated sulfonate (1). Notably, all transformations proceed efficiently to give the desired products in good yields (84%similar to 95%) and excellent selectivities (92%similar to 99% ee). The electronic properties of the arylboronic acids did not appear to affect the reactivity of the reaction. Besides, alpha,beta-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. |
| WOS关键词 | ENANTIOSELECTIVE CONJUGATE ADDITION ; ARYL BORONIC ACIDS ; VINYL SULFONES ; ORGANOBORONIC ACIDS ; GRIGNARD-REAGENTS ; ALPHA,BETA-UNSATURATED SULFONES ; ALKENYLBORONIC ACIDS ; COUPLING REACTIONS ; MICHAEL ADDITIONS ; ALPHA-KETOESTERS |
| 资助项目 | National Natural Science Foundation of China[21325209] ; Shanghai Municipal Committee of Science and Technology[14XD1404400] |
| WOS研究方向 | Chemistry |
| 语种 | 中文 |
| CSCD记录号 | CSCD:5204047 |
| WOS记录号 | WOS:000340842000007 |
| 出版者 | SCIENCE PRESS |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/276986]  |
| 专题 | 药物化学研究室 |
| 通讯作者 | Yu Yue-Na |
| 作者单位 | Chinese Acad Sci, Shanghai Inst Mat Med, Shanghai 201203, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yu Yue-Na,Xu Ming-Hua. Chiral Phosphite-Olefin Ligands: Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to beta-Aryl-alpha,beta-unsaturated Sulfonates[J]. ACTA CHIMICA SINICA,2014,72(7):815-819. |
| APA | Yu Yue-Na,&Xu Ming-Hua.(2014).Chiral Phosphite-Olefin Ligands: Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to beta-Aryl-alpha,beta-unsaturated Sulfonates.ACTA CHIMICA SINICA,72(7),815-819. |
| MLA | Yu Yue-Na,et al."Chiral Phosphite-Olefin Ligands: Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to beta-Aryl-alpha,beta-unsaturated Sulfonates".ACTA CHIMICA SINICA 72.7(2014):815-819. |
入库方式： OAI收割
来源：上海药物研究所
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