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

doi:10.6023/A14060436

	Chiral Phosphite-Olefin Ligands: Application in Rh-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to beta-Aryl-alpha,beta-unsaturated Sulfonates
	Yu Yue-Na; Xu Ming-Hua
刊名	ACTA CHIMICA SINICA
	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.
资助项目	National Natural Science Foundation of China[21325209] ; Shanghai Municipal Committee of Science and Technology[14XD1404400]
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
WOS研究方向	Chemistry
语种	中文
CSCD记录号	CSCD:5204047
出版者	SCIENCE PRESS
WOS记录号	WOS:000340842000007
内容类型	期刊论文
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.