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Download fileAcid- and Base-Switched Palladium-Catalyzed γ‑C(sp3)–H Alkylation and Alkenylation of Neopentylamine
journal contribution
posted on 21.04.2021, 18:34 authored by Jinquan Zhang, Shuaizhong Zhang, Hongbin ZouThe
functionalization of remote unactivated C(sp3)–H
and the reaction selectivity are among the core pursuits for transition-metal
catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)–H-selective alkylation and alkenylation with removable
7-azaindole as a directing group. Acid and base were found to be the
decisive regulators for the selective alkylation and alkenylation,
respectively, on the same single substrate under otherwise the same
reaction conditions. Various acrylates were compatible for the formation
of C(sp3)–C(sp3) and C(sp3)–C(sp2) bonds. The alkenylation protocol could
be further extended to acrylates with natural product units and α,β-unsaturated
ketones. The preliminary synthetic manipulation of the alkylation
and alkenylation products demonstrates the potential of this strategy
for structurally diverse aliphatic chain extension and functionalization.
Mechanistic experimental studies showed that the acidic and basic
catalytic transformations shared the same six-membered dimer palladacycle.