Stereoconvergent Arylations and Alkenylations of Unactivated Alkyl Electrophiles: Catalytic Enantioselective Synthesis of Secondary Sulfonamides and Sulfones

被引:114
作者
Choi, Junwon [1 ,2 ]
Martin-Gago, Pablo [1 ]
Fu, Gregory C. [1 ]
机构
[1] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA
[2] MIT, Dept Chem, Cambridge, MA 02139 USA
基金
美国国家卫生研究院;
关键词
CROSS-COUPLING REACTIONS; SUZUKI REACTIONS; HALIDES; DERIVATIVES; CHLORIDES; DESIGN;
D O I
10.1021/ja506885s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The development of efficient methods for the generation of enantioenridied sulfonamides and sulfones is an important objective for fields such as organic synthesis and medicinal chemistry; however, there have been relatively few reports of direct catalytic asymmetric approaches to controlling the stereochemistry of the sulfur-bearing carbon of such targets. In this report, we describe nickel-catalyzed stereo-convergent Negishi arylations and alkenylations of racemic alpha-bromosulfonamides and -sulfones that furnish the desired cross-coupling product in very good ee and yield for an array of reaction partners. Mechanistic studies are consistent with the generation of a radical intermediate that has a sufficient lifetime to diffuse out of the solvent cage and to cyclize onto a pendant olefin.
引用
收藏
页码:12161 / 12165
页数:5
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