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

Supplementary material

Supporting Info
experimental procedures, analytical data, computational details, copies of X-ray crystal structure reports, copies of NMR spectra
(±)-4l’_[O].cif
Crystallographic Information File for (±)-4l’_[O]
(±)-6.cif
Crystallographic Information File for (±)-6
S6.cif
Crystallographic Information File for S6
S17.cif
Crystallographic Information File for S17
S18.cif
Crystallographic Information File for S18
S23.cif
Crystallographic Information File for S23
S28.cif
Crystallographic Information File for S28