Rh-catalyzed ortho-selective C-H borylation of N-functionalized arenes with silica-supported bridgehead monophosphine ligands

Soichiro Kawamorita; Tatsuya Miyazaki; Hirohisa Ohmiya; Tomohiro Iwai; Masaya Sawamura

doi:10.1021/ja208364a

Rh-catalyzed ortho-selective C-H borylation of N-functionalized arenes with silica-supported bridgehead monophosphine ligands

J Am Chem Soc. 2011 Dec 7;133(48):19310-3. doi: 10.1021/ja208364a. Epub 2011 Nov 11.

Authors

Soichiro Kawamorita¹, Tatsuya Miyazaki, Hirohisa Ohmiya, Tomohiro Iwai, Masaya Sawamura

Affiliation

¹ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.

PMID: 22047192
DOI: 10.1021/ja208364a

Abstract

Supported phosphine-Rh systems, prepared in situ from silica-supported bridgehead monophosphines and [Rh(OH)(cod)](2), have enabled ortho-selective C-H borylation for a range of arenes containing nitrogen-based directing groups. The regioselectivity was excellent with various N-directing groups, including saturated and unsaturated N-heterocycles, tert-aminoalkyl groups, and imine-type C-N double bonds. The reaction showed significant tolerance toward steric repulsion around the reacting C-H bond. This Rh catalysis complements the Ir-catalyzed ortho-borylation, which is effective for arenes with oxygen-based directing groups.