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Published August 27, 2014 | Supplemental Material + Published
Journal Article Open

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

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.

Additional Information

© 2014 American Chemical Society. ACS AuthorChoice + 12, Open Access on 08/15/2015. Received: July 8, 2014; Published: August 15, 2014. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871), the Kwanjeong Educational Foundation (fellowship for J.C.), and MICINN (fellowship for P.M.-G.). We thank Dr. Ashraf Wilsily, Dr. Nathan D. Schley, Dr. David VanderVelde (Caltech NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance and for helpful discussions.

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Supplemental Material - ja506885s_si_001.cif

Supplemental Material - ja506885s_si_002.pdf

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