Mechanisms for C(sp2)–Si activation of aryltrimethylsilyl groups in palladium-catalysed couplings. Issue 38 (19th September 2017)

• Record Type: Journal Article
• Authors: Rauf, Waqar; Brown, John M.
• Is Part Of: Organic & biomolecular chemistry. Volume 15:Issue 38(2017)
• Page Start: 8179
• Page End: 8185
• Publication Date: 2017-09-19
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c7ob01675a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : DFT reveals why arenes with an amide or anilide directing group react faster by C–Si than by C–H cleavage in Pd coupling reactions. 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.