Issue 44, 2020

Decarbonylative ether dissection by iridium pincer complexes

Abstract

A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(I) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C–C bond, one C–O bond, and two C–H bonds, along with formation of two new C–H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(III) complex containing an aza-18-crown-6 ether macrocycle. Intramolecular cleavage of macrocyclic and acyclic ethers was also found in analogous complexes featuring aza-15-crown-5 ether or bis(2-methoxyethyl)amino groups. Intermolecular decarbonylation of cyclic and linear ethers was observed when diethylaminophenylphosphinite iridium(I) dinitrogen or norbornene complexes were employed. Mechanistic studies reveal the nature of key intermediates along a pathway involving initial iridium(I)-mediated double C–H bond activation.

Graphical abstract: Decarbonylative ether dissection by iridium pincer complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Jul 2020
Accepted
24 Sep 2020
First published
24 Sep 2020
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., 2020,11, 12130-12138

Decarbonylative ether dissection by iridium pincer complexes

C. Yoo, H. M. Dodge, A. H. Farquhar, K. E. Gardner and A. J. M. Miller, Chem. Sci., 2020, 11, 12130 DOI: 10.1039/D0SC03736B

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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