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

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• 作者：V.D. Vijaykumar Bodduri^a ; Kyung-Min Choi^a ; Raghavender Rao Vaidya^a ; Kalpesh Patil^a ; Sridhar Chirumarry^a ; Kiwan Jang^b ; Yong-Jin Yoon^c ; John R. Falck^d ; Dong-Soo Shin^a ; ^{dsshin@changwon.ac.kr" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Iron powder ; Acylative ether cleavage ; Single electron transfer ; SN1 mechanism ; Chloroesters
• 刊名：Tetrahedron Letters
• 出版年：2015
• 出版时间：23 December 2015
• 年：2015
• 卷：56
• 期：51
• 页码：7089-7093
• 全文大小：4382 K

文摘

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.