1,2‐Silyl migration in 1‐halonaphthalenes catalyzed by I₂

Abstract

1‐Halo‐8‐hydrosilylnaphthalenes undergo 1,2‐silyl migration to form 1‐halo‐7‐silylnaphthalenes. The influence of the substituents on the silicon atom, the solvent effect, and the D‐labeling experiments are investigated. The migration process may include four steps: (a) generation of acid (HI) by the reaction of the hydrosilane with I2, (b) protonation of the naphthalene ring, (c) silyl group migration in the protonated intermediate, and (d) deprotonation of the naphthalene ring.

Alkyne Linchpin Strategy for Drug:Pharmacophore Conjugation: Experimental and Computational Realization of a Meta-Selective Inverse Sonogashira Coupling

“…[31][32][33][34][35] In many systems, silver salt plays an essential role in enhancing the reaction rate and/or yields. Various roles of silver carboxylate AgCOOR salts in such reactions have been proposed: (1) they serve as a source of carboxylate for the Pd(II) metal-centre, participating in carboxylate-assisted concerted metalation deprotonation (CMD) in the C-H activation step; [35][36][37][38][39] (2) they act as a terminal oxidant to regenerate Pd(II) catalyst; [40][41][42] (3) they form heterometallic Pd−Ag complexes that facilitate C−H activation; 40,43,44 (4) they directly activate C−H bond forming Ag-C intermediate; 45,46 (5) they act as halide scavengers in PdX (X = halide) complex after the reductive elimination step. 47 The experimental work to establish the exact role of these silver additives are rare and an understanding of their exact roles in the mechanistic picture is rather incomplete.…”