Halogenation through Deoxygenation of Alcohols and Aldehydes

Jia Chen, Jin-Hong Lin and Ji-Chang Xiao*

*Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China, Email: jchxiaosioc.ac.cn

J. Chen, J.-H. Lin, J.-C. Xiao, Org. Lett., 2018, 20, 3061-3064.

DOI: 10.1021/acs.orglett.8b01058

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Abstract

The combination of Ph₃P and easily available 1,2-dihaloethanes (XCH₂CH₂X; X = Cl, Br, or I), was very effective for a mild deoxygenative halogenation of alcohols and aldehydes. The use of (EtO)₃P instead of Ph₃P enables a convenient purification process, as the byproduct (EtO)₃P═O could be removed by aqueous washing. A dehydroxy-fluorination proceeds well in the presence of ICH₂CH₂I and CsF as fluoride source in DMF.

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proposed mechanism

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Key Words

Appel reaction, 1,1-dibromides, 1,1-dichlorides, benzyl chlorides, benzyl bromides, benzyl iodides, alkyl chlorides, alkyl bromides, alkyl iodides

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ID: J54-Y2018