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Transfer Vinylation and Dienylation via Rhodium(I)-Catalyzed Deketonation of Allylic Alcohols

Zheng‐Qiang Liu, Cheng Liang, Zhen Luo, Yufei Wu, Chuan‐Ming Hong, Qinghua Li, Tang‐Lin Liu

2022ACS Catalysis18 citationsDOI

Abstract

The C–O and C–H bond cleavages of simple allylic alcohols have witnessed tremendous progress in recent years. However, an efficient method for cleaving the C–C bond via β-carbon elimination is still comparatively underexploited. In this study, we demonstrate rhodium(I)-catalyzed deketonative transfer vinylation and transfer dienylation of various tertiary allylic alcohols with ketones via β-vinyl and β-dienyl elimination. Under mild reaction conditions, allylic and dienyl alcohols with quaternary centers were thus selectively and efficiently constructed in moderate to good yields. The methodologies of transfer vinylation and transfer dienylation, which would provide access to a range of useful organic compounds, pave a significant way for transition-metal-catalyzed C–C activation in organic synthesis.

Topics & Concepts

Allylic rearrangementRhodiumChemistryCatalysisOrganic synthesisOrganic chemistryCombinatorial chemistryDouble bondTransfer hydrogenationRutheniumCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisCatalytic Cross-Coupling Reactions
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