Issue 7, 2019

Selective alkyl ether cleavage by cationic bis(phosphine)iridium complexes

Abstract

Catalysts capable of heterolytic silane activation have been successfully applied to the conversion of alkyl ethers to silyl ethers via C–O bond cleavage. The previously-reported cationic pincer-supported iridium complex for this transformation suffers from poor selectivity with regard to monodealkylation of substrate ethers. We demonstrate that a simple non-pincer iridium complex offers improved selectivity and is capable of benzylic ether cleavage in the presence of reductively-labile alkyl and aryl halide functionality. Preliminary mechanistic experiments suggest a neutral tetrahydridosilyliridium resting state which is consistent with previous mechanistic hypotheses. These experiments suggest that a pincer ligand framework is not required for activity in ether cleavage reactions and that simple cationic bis(phosphine)iridium complexes may offer improved selectivity profiles for applications to more-complex substrate molecules.

Graphical abstract: Selective alkyl ether cleavage by cationic bis(phosphine)iridium complexes

Supplementary files

Article information

Article type
Communication
Submitted
17 sept. 2018
Accepted
31 oct. 2018
First published
31 oct. 2018

Org. Biomol. Chem., 2019,17, 1744-1748

Selective alkyl ether cleavage by cationic bis(phosphine)iridium complexes

C. A. H. Jones and N. D. Schley, Org. Biomol. Chem., 2019, 17, 1744 DOI: 10.1039/C8OB02298D

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