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Catalytic activation of unstrained C(aryl)-C(aryl) bonds in 2,2'-biphenols.

ABSTRACT: Transition metal catalysis has emerged as an important means for C-C activation that allows mild and selective transformations. However, the current scope of C-C bonds that can be activated is primarily restricted to either highly strained systems or more polarized C-C bonds. In contrast, the catalytic activation of non-polar and unstrained C-C moieties remains an unmet challenge. Here we report a general approach for the catalytic activation of the unstrained C(aryl)-C(aryl) bonds in 2,2'-biphenols. The key is to utilize the phenol moiety as a handle to install phosphinites as a recyclable directing group. Using hydrogen gas as the reductant, monophenols are obtained with a low catalyst loading and high functional group tolerance. This approach is also applied to the synthesis of 2,3,4-trisubstituted phenols. A further mechanistic study suggests that the C-C activation step is mediated by a rhodium(I) monohydride species. Finally, a preliminary study on breaking the inert biphenolic moieties in lignin models is illustrated.

SUBMITTER: Zhu J

PROVIDER: S-EPMC6383370 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Catalytic activation of unstrained C(aryl)-C(aryl) bonds in 2,2'-biphenols.

Zhu Jun J Wang Jianchun J Dong Guangbin G

Nature chemistry 20181105 1

Transition metal catalysis has emerged as an important means for C-C activation that allows mild and selective transformations. However, the current scope of C-C bonds that can be activated is primarily restricted to either highly strained systems or more polarized C-C bonds. In contrast, the catalytic activation of non-polar and unstrained C-C moieties remains an unmet challenge. Here we report a general approach for the catalytic activation of the unstrained C(aryl)-C(aryl) bonds in 2,2'-biphe ...[more]

PMID: 30397321

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