Palladium-catalyzed intramolecular reductive cross-coupling of Csp2-Csp3 bond formation

Hui Liu; Jianpeng Wei; Zongjun Qiao; Yana Fu; Xuefeng Jiang

doi:10.1002/chem.201403093

Palladium-catalyzed intramolecular reductive cross-coupling of Csp2-Csp3 bond formation

Chemistry. 2014 Jul 1;20(27):8308-13. doi: 10.1002/chem.201403093. Epub 2014 May 28.

Authors

Hui Liu¹, Jianpeng Wei, Zongjun Qiao, Yana Fu, Xuefeng Jiang

Affiliation

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062 (P. R. China); School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (P. R. China).

PMID: 24889494
DOI: 10.1002/chem.201403093

Abstract

A Pd-catalyzed efficient reductive cross-coupling reaction without metallic reductant to construct a Csp(2) -Csp(3) bond has been reported. A Pd(IV) complex was proposed to be a key intermediate, which subsequently went through double oxidative addition and double reductive elimination to produce the cross-coupling products by involving Pd(0/II/IV) in one transformation. The oxidative addition from Pd(II) to Pd(IV) was partially demonstrated to be a radical process by self-oxidation of substrate without additional oxidants. Furthermore, the solvent was proved to be the reductant for this transformation through XPS analysis.

Keywords: C-C bond formation; Csp3X bond; catalysis; cross-coupling; palladium.