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Carboxylate‐Assisted Oxidative Addition to Aminoalkyl Pd II Complexes: C(sp 3 )−H Arylation of Alkylamines by Distinct Pd II /Pd IV Pathway
Author(s) -
Whitehurst William G.,
Blackwell J. Henry,
Hermann Gary N.,
Gaunt Matthew J.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201902838
Subject(s) - chemistry , carboxylate , reagent , aryl , catalysis , medicinal chemistry , oxidative phosphorylation , oxidative addition , combinatorial chemistry , stoichiometry , primary (astronomy) , stereochemistry , organic chemistry , biochemistry , alkyl , physics , astronomy
Reported is the discovery of an approach to functionalize secondary alkylamines using 2‐halobenzoic acids as aryl‐transfer reagents. These reagents promote an unusually mild carboxylate‐assisted oxidative addition to alkylamine‐derived palladacycles. In the presence of Ag I salts, a decarboxylative C(sp 3 )−C(sp 2 ) bond reductive elimination leads to γ‐aryl secondary alkylamines and renders the carboxylate motif a traceless directing group. Stoichiometric mechanistic studies were effectively translated to a Pd‐catalyzed γ‐C(sp 3 )−H arylation process for secondary alkylamines.