Issue 16, 2018

Pd(ii)-catalyzed synthesis of bifunctionalized carboranes via cage B–H activation of 1-CH2NH2-o-carboranes

Abstract

Aminoalkyl carboranes are anticipated to be valuable synthons toward the synthesis of bifunctionalized carboranes. However, direct cage boron derivation of these carborane derivatives has not been solved. Herein, the reversible conversion of catalytically infeasible o-carboranyl methylamines (1-CH2NH2-o-carboranes) into bidentate imines initiates Pd-mediated cage B–H activation. As a result, an amine coordinated bicyclic Pd(II) complex (3) has been isolated and proven to be the catalytically active intermediate for highly site-selective B–H diarylation of o-carboranyl methylamines. Using glyoxylic acid as an inexpensive and commercially available transient directing reagent, a wide range of cage B(4,5)-diarylated free primary o-carboranyl methylamines were prepared in good to excellent yields with the avoidance of the pre-installation and removal of a directing group. This method provides easy access to cage boron functionalized o-carboranyl methylamines with potential for application in pharmaceuticals.

Graphical abstract: Pd(ii)-catalyzed synthesis of bifunctionalized carboranes via cage B–H activation of 1-CH2NH2-o-carboranes

Supplementary files

Article information

Article type
Edge Article
Submitted
12 Marts 2018
Accepted
26 Marts 2018
First published
27 Marts 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 3964-3969

Pd(II)-catalyzed synthesis of bifunctionalized carboranes via cage B–H activation of 1-CH2NH2-o-carboranes

X. Zhang and H. Yan, Chem. Sci., 2018, 9, 3964 DOI: 10.1039/C8SC01154K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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