Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles

Keke Meng, Tingyan Li, Chunbing Yu, Cong Shen, Jian Zhang () and Guofu Zhong ()
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Keke Meng: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University
Tingyan Li: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University
Chunbing Yu: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University
Cong Shen: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University
Jian Zhang: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University
Guofu Zhong: College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract Great efforts have been made in the activation of a C(alkenyl)-H bond vicinal to the directing group to proceed via five- or six-membered endo-metallocycles. In stark contrast, functionalization of a C(alkenyl)-H bond geminal to the directing group via exo-metallocycle pathway continued to be elusive. Here we report the selective transformation of an olefinic C-H bond that is geminal to the directing group bearing valuable hydroxyl, carbamate or amide into a C-C bond, which proceeds through four- to eight-membered exo-palladacycles. Compared to the reported mechanisms proceeding only through six-membered exo-palladacycles via N,N-bidentate chelation, our weak and O-monodentate chelation-assisted C(alkenyl)-H activations tolerate longer or shorter distances between the olefinic C-H bonds and the coordinating groups, allowing for the functionalizations of many olefinic C-H bonds in alkenyl alcohols, carbamates and amides. The synthetic applicability has been demonstrated by the preparative scale and late-stage C-H functionalization of steroid and ricinoleate derivatives.

Date: 2019
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DOI: 10.1038/s41467-019-13098-1

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