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Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums
Author(s) -
Erdelmeier Irene,
Won Joonghee,
Park Steve,
Decker Jürgen,
Bülow Gerd,
Baik MuHyun,
Gais HansJoachim
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201904862
Subject(s) - phosphine , carbene , chemistry , reagent , catalysis , combinatorial chemistry , lithium (medication) , catalytic cycle , ligand (biochemistry) , nickel , walden inversion , carbenoid , alkylation , medicinal chemistry , computational chemistry , stereochemistry , organic chemistry , medicine , biochemistry , receptor , rhodium , endocrinology
The mechanistic platform for a novel nickel 0 ‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni 0 ‐catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp 2 organolithiums and sp 2 and sp 3 Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni 0 ‐catalyst and precatalyst Ni(PPh 3 ) 2 Cl 2 afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni 0 ‐catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5‐cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni 0 ‐vinylidene intermediate through an indispensable electron‐rich Ni 0 ‐center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni 0 ‐vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni‐complex and ultimately racemic alkenyllithium.