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

V. D Vijaykumar Bodduri; Kyung Min Choi; Raghavender Rao Vaidya; Kalpesh Patil; Sridhar Chirumarry; Kiwan Jang; Yong Jin Yoon; J R Falck; Dong Soo Shin

doi:10.1016/j.tetlet.2015.11.016

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

V. D Vijaykumar Bodduri, Kyung Min Choi, Raghavender Rao Vaidya, Kalpesh Patil, Sridhar Chirumarry, Kiwan Jang, Yong Jin Yoon, J R Falck, Dong Soo Shin

Biochemistry

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

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 S_N1 dissociative pathway.

Original language	English (US)
Pages (from-to)	7089-7093
Number of pages	5
Journal	Tetrahedron Letters
Volume	56
Issue number	51
DOIs	https://doi.org/10.1016/j.tetlet.2015.11.016
State	Published - Dec 23 2015

Keywords

Acylative ether cleavage
Chloroesters
Iron powder
S1 mechanism
Single electron transfer

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2015.11.016

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title = "An efficient iron catalyzed regioselective acylative cleavage of ethers: Scope and mechanism",

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.",

keywords = "Acylative ether cleavage, Chloroesters, Iron powder, S1 mechanism, Single electron transfer",

author = "Bodduri, {V. D Vijaykumar} and Choi, {Kyung Min} and Vaidya, {Raghavender Rao} and Kalpesh Patil and Sridhar Chirumarry and Kiwan Jang and Yoon, {Yong Jin} and Falck, {J R} and Shin, {Dong Soo}",

note = "Funding Information: 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 T{\'o}th, University of Pannonia, Veszpr{\'e}m, Hungary for fruitful discussion. Publisher Copyright: {\textcopyright} 2015 Published by Elsevier Ltd.",

year = "2015",

month = dec,

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doi = "10.1016/j.tetlet.2015.11.016",

language = "English (US)",

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TY - JOUR

T1 - An efficient iron catalyzed regioselective acylative cleavage of ethers

T2 - Scope and mechanism

AU - Bodduri, V. D Vijaykumar

AU - Choi, Kyung Min

AU - Vaidya, Raghavender Rao

AU - Patil, Kalpesh

AU - Chirumarry, Sridhar

AU - Jang, Kiwan

AU - Yoon, Yong Jin

AU - Falck, J R

AU - Shin, Dong Soo

N1 - Funding Information: 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. Publisher Copyright: © 2015 Published by Elsevier Ltd.

PY - 2015/12/23

Y1 - 2015/12/23

N2 - 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.

AB - 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.

KW - Acylative ether cleavage

KW - Chloroesters

KW - Iron powder

KW - S1 mechanism

KW - Single electron transfer

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DO - 10.1016/j.tetlet.2015.11.016

M3 - Article

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SN - 0040-4039

VL - 56

SP - 7089

EP - 7093

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 51

ER -

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

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