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无金属参与的、区域和立体选择性的炔酮和炔酰胺的氯化氢和溴化氢反应。

Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides.

机构信息

College of Chemistry, Chemical Engineering and Biotechnology, Donghua University , 2999 North Renmin Lu, Shanghai 201620, China.

Department of Chemistry, University of Louisville , Louisville, Kentucky 40292, United States.

出版信息

J Org Chem. 2017 Dec 15;82(24):13179-13187. doi: 10.1021/acs.joc.7b02257. Epub 2017 Dec 7.

DOI:10.1021/acs.joc.7b02257
PMID:29166765
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5735994/
Abstract

We developed an atom-economical and metal-free method for the regio- and stereo-selective hydrohalogenation of ynones and ynamides using easy to handle DMPU/HX (X = Br or Cl) reagents. The reaction operates under mild conditions and a range of functional groups is well tolerated. We propose that the hydrohalogenation of ynones gives the anti-addition products via a concerted multimolecular Ad3 mechanism and that the hydrohalogenation of ynamides produces the syn-addition products via a cationic keteniminium intermediate.

摘要

我们开发了一种原子经济性且无金属的方法，用于使用易于处理的 DMPU/HX（X = Br 或 Cl）试剂对炔酮和炔酰胺进行区域和立体选择性氢卤化。该反应在温和的条件下进行，并且可以很好地耐受各种官能团。我们提出炔酮的氢卤化通过协同多分子 Ad3 机理生成反加成产物，而炔酰胺的氢卤化通过阳离子烯酮亚胺中间体生成顺加成产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/c531b074b41d/jo-2017-02257h_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/93aba2735ef4/jo-2017-02257h_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/000ac6296a82/jo-2017-02257h_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/f8c2ea9d2570/jo-2017-02257h_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/c531b074b41d/jo-2017-02257h_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/93aba2735ef4/jo-2017-02257h_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/000ac6296a82/jo-2017-02257h_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/f8c2ea9d2570/jo-2017-02257h_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7657/5735994/c531b074b41d/jo-2017-02257h_0004.jpg

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