1. Nickel-catalyzed, silyl-directed, ortho-borylation of arenes via an unusual Ni(II)/Ni(IV) catalytic cycle.
- Author
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Su, Xiaoshi, Li, Guoao, He, Linke, Chen, Shengda, Yang, Xiaoliang, Wang, Guoqiang, and Li, Shuhua
- Subjects
METAL catalysts ,PRECIOUS metals ,BORYLATION ,AROMATIC compounds ,HETEROCYCLIC compounds ,NICKEL catalysts - Abstract
Nickel-catalyzed C–H bond functionalization reactions provide an impressive alternative to those with noble metal catalysts due to their unique reactivity and low cost. However, the regioselective C(sp
2 )–H borylation reaction of arenes accomplished by nickel catalyst remains limited. We herein disclose a silyl-directed ortho C(sp2 )–H borylation of substituted arenes with a Ni(cod)2 /PMe3 /KHMDS catalyst system. Using readily available starting materials, this protocol provides easy access to ortho-borylated benzylic hydrosilanes bearing flexible substitution patterns. These products can serve as versatile building blocks for the synthesis of sila or sila/borine heterocycles under mild conditions. Control experiments and DFT calculations suggest that a catalytic amount of base prompts the formation of Ni(II)-Bpin-ate complex, likely related to the C(sp2 )–H bond activation. This borylation reaction might follow an unusual Ni(II)/Ni(IV) catalytic cycle. Nickel-catalyzed C–H bond functionalization reactions provide an impressive alternative to those with noble metal catalysts but the regioselective C(sp2 )−H borylation reaction of arenes accomplished by nickel catalyst remains challenging. Here the authors disclose a silyl-directed ortho C(sp2 )−H borylation of substituted arenes with a Ni(cod)2 /PMe3 /KHMDS catalyst system. [ABSTRACT FROM AUTHOR]- Published
- 2024
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