Issue 38, 2017

Mechanisms for C(sp2)–Si activation of aryltrimethylsilyl groups in palladium-catalysed couplings

Abstract

Silyl-substituted aromatic compounds can participate as the electrophilic component in palladium-catalysed cross-couplings, and reactivity is enhanced by a neighbouring silyl-group. Products analogous to those obtained from C–H activation chemistry are accessible by this means with the additional benefit of regiochemistry defined by the site of silyl substitution. DFT studies described here show that the mechanism of C–Si cleavage is distinct from previously recognised mechanisms for C–H cleavage, with a cascade of silyl intermediates en route to a stable product. The amide directing-groups are involved only in the stabilisation of palladacyclic intermediates, and are never disposed to activate silicon directly. 5-Membered and 6-membered palladacycles are known to behave differently in coupling reactions and the calculations reveal underlying reasons in the cationic pathways studied here.

Graphical abstract: Mechanisms for C(sp2)–Si activation of aryltrimethylsilyl groups in palladium-catalysed couplings

Supplementary files

Article information

Article type
Paper
Submitted
07 Jūl. 2017
Accepted
08 Sept. 2017
First published
19 Sept. 2017

Org. Biomol. Chem., 2017,15, 8179-8185

Mechanisms for C(sp2)–Si activation of aryltrimethylsilyl groups in palladium-catalysed couplings

W. Rauf and J. M. Brown, Org. Biomol. Chem., 2017, 15, 8179 DOI: 10.1039/C7OB01675A

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