Metal-Free Halogenation of N-Substituted Enaminoesters and Enaminones: A Facile Access to Functionalized α,α-Dihaloimines

Changfu Qiu; Heshui Yu; Chuanjiang Qiu; Fangyi Li; Tongchuan Suo; Chunhua Wang; Songtao Bie; Zheng Li

doi:10.1055/s-0039-1690819

Synthesis, Table of Contents

Synthesis 2020; 52(08): 1301-1314
DOI: 10.1055/s-0039-1690819

paper

Metal-Free Halogenation of N-Substituted Enaminoesters and Enaminones: A Facile Access to Functionalized α,α-Dihaloimines

Changfu Qiu

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Heshui Yu

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Chuanjiang Qiu

^bChemistry Manufacture Control Department, Accendatech Co., Ltd., Tianjin 300384, P. R. of China

,

Fangyi Li ∗

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Tongchuan Suo

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Chunhua Wang

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Songtao Bie

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

,

Zheng Li∗

^aCollege of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 301617, P. R. of China Email: lifangyi@tjutcm.edu.cn Email: lizheng@tjutcm.edu.cn

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Abstract

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Abstract

An efficient and general method for the synthesis of functionalized α,α-dihaloimines via halogenation of N-substituted enaminoesters and enaminones is described. This reaction, in which both α,α-dihaloimines and mixed α,α-dihaloimines could be achieved in good to excellent yields, is believed to proceed via an α-monohalogenated enamine intermediate. This synthetic method features no use of transition metals, readily accessible substrates, mild reaction conditions, simple and safe operation, and gram scale synthesis. Furthermore, the synthetic utility of the products was demonstrated by their efficient transformations to further useful nitrogen-containing heterocycles and building blocks.

Key words

functionalized α,α-dihaloimines - halogenation - enaminoesters - enaminones - metal free - N-heterocycles

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References

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