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Diazaphosphinyl radical-catalyzed deoxygenation of α-carboxy ketones: a new protocol for chemo-selective C–O bond scission via mechanism regulation

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Abstract

C–O bond cleavage is often a key process in defunctionalization of organic compounds as well as in degradation of natural polymers. However, it seldom occurs regioselectively for different types of C–O bonds under metal-free mild conditions. Here we report a facile chemo-selective cleavage of the α-C–O bonds in α-carboxy ketones by commercially available pinacolborane under the catalysis of diazaphosphinane based on a mechanism switch strategy. This new reaction features high efficiency, low cost and good group-tolerance, and is also amenable to catalytic deprotection of desyl-protected carboxylic acids and amino acids. Mechanistic studies indicated an electron-transfer-initiated radical process, underlining two crucial steps: (1) the initiator azodiisobutyronitrile switches originally hydridic reduction to kinetically more accessible electron reduction; and (2) the catalytic phosphorus species upconverts weakly reducing pinacolborane into strongly reducing diazaphosphinane.

Graphical abstract: Diazaphosphinyl radical-catalyzed deoxygenation of α-carboxy ketones: a new protocol for chemo-selective C–O bond scission via mechanism regulation

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Article information


Submitted
09 Jun 2020
Accepted
27 Jul 2020
First published
27 Jul 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Diazaphosphinyl radical-catalyzed deoxygenation of α-carboxy ketones: a new protocol for chemo-selective C–O bond scission via mechanism regulation

J. Zhang, J. Yang and J. Cheng, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC03220D

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