Regioselectivity in C-H activation: reagent control in cyclometallation of 2-(1-naphthyl)-pyridine

Mikhail Kondrashov; David Provost; Ola F Wendt

doi:10.1039/c5dt04068j

Regioselectivity in C-H activation: reagent control in cyclometallation of 2-(1-naphthyl)-pyridine

Dalton Trans. 2016 Jan 14;45(2):525-31. doi: 10.1039/c5dt04068j.

Authors

Mikhail Kondrashov¹, David Provost¹, Ola F Wendt¹

Affiliation

¹ Centre for Analysis and Synthesis, Department of Chemistry, Lund University, P. O. Box 124, S-221 00 Lund, Sweden. Ola.Wendt@chem.lu.se.

PMID: 26597047
DOI: 10.1039/c5dt04068j

Abstract

2-(1-Naphthyl)-pyridine () possesses sp(2) C-H bonds in both the γ- and δ-positions and is therefore a suitable substrate for studying the cyclometallation selectivity with different reagents and conditions. Such selectivity studies are reported. Based on deuterium-exchange experiments it is concluded that cycloruthenation with RuCl2(p-cymene) dimer is reversible with kinetic and thermodynamic preference for γ-substitution. Electrophilic cycloborylation, on the other hand, shows unusual δ-substitution. The previously published cyclopalladation and cycloauration of the substrate was studied in detail and was shown to be irreversible; they proceed under kinetic control and give γ- and δ-substitution for palladium and gold, respectively.

Publication types

Research Support, Non-U.S. Gov't