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Regiodivergent C−H and Decarboxylative C−C Alkylation by Ruthenium Catalysis: ortho versus meta Position‐Selectivity
Author(s) -
Korvorapun Korkit,
Moselage Marc,
Struwe Julia,
Rogge Torben,
Messinis Antonis M.,
Ackermann Lutz
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202007144
Subject(s) - homolysis , ruthenium , chemistry , alkylation , reductive elimination , bond cleavage , selectivity , medicinal chemistry , stereochemistry , catalysis , organic chemistry , radical
Ruthenium(II)biscarboxylate complexes enabled the selective alkylation of C−H and C−C bonds at the ortho ‐ or meta ‐position. ortho ‐C−H Alkylations were achieved with 4‐, 5‐ as well as 6‐membered halocycloalkanes. Furthermore, the judicious choice of the directing group allowed for a full control of ortho‐/meta ‐selectivities. Detailed mechanistic studies by experiment and computation were performed and provided strong support for an oxidative addition/reductive elimination process for ortho ‐alkylations, while a homolytic C−X cleavage was operative for the meta ‐selective transformations.