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. 2014 Aug 27;136(34):12161-5.
doi: 10.1021/ja506885s. Epub 2014 Aug 15.

Stereoconvergent arylations and alkenylations of unactivated alkyl electrophiles: catalytic enantioselective synthesis of secondary sulfonamides and sulfones

Junwon Choi  1 , Pablo Martín-Gago, Gregory C Fu
Affiliations

Stereoconvergent arylations and alkenylations of unactivated alkyl electrophiles: catalytic enantioselective synthesis of secondary sulfonamides and sulfones

Junwon Choi et al. J Am Chem Soc. .

Abstract

The development of efficient methods for the generation of enantioenriched 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 stereoconvergent Negishi arylations and alkenylations of racemic α-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.

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Figures

Figure 1
Figure 1
Dependence of the ratio of uncyclized (D)/cyclized (C) product on the concentration of nickel.
See this image and copyright information in PMC

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