Ligand-Controlled NiH-Catalyzed Regiodivergent Chain-Walking Hydroalkylation of Alkenes

Lei Zhao; Yuqin Zhu; Mengyuan Liu; Leipeng Xie; Jimin Liang; Haoran Shi; Xiao Meng; Zhengyang Chen; Jian Han; Chao Wang

doi:10.1002/anie.202204716

Ligand-Controlled NiH-Catalyzed Regiodivergent Chain-Walking Hydroalkylation of Alkenes

Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202204716. doi: 10.1002/anie.202204716. Epub 2022 Jun 8.

Authors

Lei Zhao¹, Yuqin Zhu¹, Mengyuan Liu¹, Leipeng Xie¹, Jimin Liang¹, Haoran Shi¹, Xiao Meng¹, Zhengyang Chen¹, Jian Han², Chao Wang¹

Affiliations

¹ Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin, 300387, P. R. China.
² State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.

PMID: 35608276
DOI: 10.1002/anie.202204716

Abstract

A NiH-catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand-controlled, directing group-assisted strategy, various alkyl units are site-selectively installed at inert sp³ C-H sites far away from the original C=C bonds. A range of structurally diverse α- and β-branched protected amines are conveniently synthesized via stabilization of 5- and 6-membered nickelacycles respectively. This method exhibits broad scope and high functional group tolerance, and can be applied to late-stage modification of medicinally relevant molecules.

Keywords: Alkenes; Chain-Walking; Directing Groups; Nickel Catalysis; Regiodivergent.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Alkenes*
Amines*
Catalysis
Ligands
Molecular Structure
Stereoisomerism

Substances

Alkenes
Amines
Ligands