Elsevier

Tetrahedron Letters

Volume 56, Issue 51, 23 December 2015, Pages 7089-7093
Tetrahedron Letters

An efficient iron catalyzed regioselective acylative cleavage of ethers: scope and mechanism

https://doi.org/10.1016/j.tetlet.2015.11.016Get rights and content

Abstract

A method involving iron catalyzed acylative cleavage of cyclic and acyclic ethers with acyl/aroyl chlorides has been studied to produce chloroesters and esters respectively. Examination of the scope revealed that less electron rich alkyl group in unsymmetric, acyclic ether was acylated while the chloride derived from the counterpart moiety was volatile and difficult to isolate. In contrast, α-branched cyclic ethers were converted to the corresponding primary ester and secondary chloride. Steric hindrance of ether also plays an important role in acylative C–O bond cleavage. The mechanism of ether cleavage is proposed to involve a single electron initiated SN1 dissociative pathway.

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Acknowledgements

This work was partially supported by the grants from Korea Ministry of Environment (KME, 412-111-008) and the National Research Foundation of Korea (NRF-2010-0029634). J.R.F. was supported by the Robert A. Welch Foundation (I-0011). The authors thank Dr. Imre Tóth, University of Pannonia, Veszprém, Hungary for fruitful discussion.

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