Catalysis

Electrophilic Sulfur Reagent Design Enables Catalytic syn-Carbosulfenylation of Unactivated Alkenes

Authors

Abstract

A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored organosulfur electrophiles. Key to the development of this transformation is the identification of a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family of sulfur electrophiles. Tuning the electronic and steric properties of the leaving group in these reagents controls pathway selectivity, favoring three-component coupling and suppressing side reactions, as examined via computational studies. The unique syn-stereoselectivity differs from traditional electrophilic sulfenyl transfer processes involving a thiiranium ion intermediate and arises from the directed arylnickel(I) migratory insertion mechanism, as elucidated through reaction kinetics and control experiments. Reactivity and regioselectivity are facilitated by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, alcohols, amines, amides, and azaheterocycles.

Content

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Supplementary material

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Supporting Info
experimental procedures, analytical data, computational details, copies of X-ray crystal structure reports, copies of NMR spectra
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Crystallographic Information File for (±)-4l’_[O]
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Crystallographic Information File for (±)-6
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