Issue 18, 2022

What is the difference between mono- and biphosphine ligands? Revealing the chemoselectivity in Pd-catalysed carbenation of bromonaphthalene

Abstract

Ligand-controlled chemoselectivity is an important topic in organometallic chemistry. In this work, DFT calculations were used to reveal the chemoselectivity of a Pd-catalysed three-component dearomative carbenation of bromonaphthalene with diazo compounds and allylborates. When a monophosphine ligand was used, ligand exchange with a diazo compound was favored by the release of a phosphine ligand. Therefore, a three-component coupling reaction could occur. However, when a biphosphine ligand was used, ligand exchange between the phosphine and the diazo compounds was difficult. Therefore, the Suzuki–Miyaura coupling product was observed in this case, without the participation of the carbene moiety.

Graphical abstract: What is the difference between mono- and biphosphine ligands? Revealing the chemoselectivity in Pd-catalysed carbenation of bromonaphthalene

Supplementary files

Article information

Article type
Research Article
Submitted
06 Jun 2022
Accepted
27 Jul 2022
First published
02 Aug 2022

Org. Chem. Front., 2022,9, 4916-4923

What is the difference between mono- and biphosphine ligands? Revealing the chemoselectivity in Pd-catalysed carbenation of bromonaphthalene

W. Gong, D. Fu, K. Zhong, H. Ni, X. He, C. Shan, R. Li and Y. Lan, Org. Chem. Front., 2022, 9, 4916 DOI: 10.1039/D2QO00910B

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