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C2-selective alkylation of pyridines by rhodium–aluminum complexes

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Abstract A C2- and mono-selective alkylation of various pyridines and azines with unactivated alkenes and vinylarenes using a heterobimetallic Rh–Al catalyst is reported. The use of aliphatic alkenes exclusively affords… Click to show full abstract

Abstract A C2- and mono-selective alkylation of various pyridines and azines with unactivated alkenes and vinylarenes using a heterobimetallic Rh–Al catalyst is reported. The use of aliphatic alkenes exclusively affords the linear alkylation products, while vinylarenes mainly afford branched alkylation products. The details of the reaction mechanism were revealed by DFT calculations: the reductive elimination of the products is rate-determining, which is consistent with the experimental results. The origin of the linear/branched selectivity was elucidated based on deformation/interaction analysis.

Keywords: alkylation pyridines; rhodium aluminum; selective alkylation; alkylation; aluminum complexes; pyridines rhodium

Journal Title: Tetrahedron
Year Published: 2021

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