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

[Image: see text] 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. W...

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Detalles Bibliográficos
Autores principales: Zeng, Xiaojun, Lu, Zhichao, Liu, Shiwen, Hammond, Gerald B., Xu, Bo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5735994/
https://www.ncbi.nlm.nih.gov/pubmed/29166765
http://dx.doi.org/10.1021/acs.joc.7b02257
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author Zeng, Xiaojun
Lu, Zhichao
Liu, Shiwen
Hammond, Gerald B.
Xu, Bo
author_facet Zeng, Xiaojun
Lu, Zhichao
Liu, Shiwen
Hammond, Gerald B.
Xu, Bo
author_sort Zeng, Xiaojun
collection PubMed
description [Image: see text] 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 Ad(E)3 mechanism and that the hydrohalogenation of ynamides produces the syn-addition products via a cationic keteniminium intermediate.
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spelling pubmed-57359942018-11-23 Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides Zeng, Xiaojun Lu, Zhichao Liu, Shiwen Hammond, Gerald B. Xu, Bo J Org Chem [Image: see text] 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 Ad(E)3 mechanism and that the hydrohalogenation of ynamides produces the syn-addition products via a cationic keteniminium intermediate. American Chemical Society 2017-11-23 2017-12-15 /pmc/articles/PMC5735994/ /pubmed/29166765 http://dx.doi.org/10.1021/acs.joc.7b02257 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Zeng, Xiaojun
Lu, Zhichao
Liu, Shiwen
Hammond, Gerald B.
Xu, Bo
Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title_full Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title_fullStr Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title_full_unstemmed Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title_short Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides
title_sort metal-free, regio-, and stereo-controlled hydrochlorination and hydrobromination of ynones and ynamides
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5735994/
https://www.ncbi.nlm.nih.gov/pubmed/29166765
http://dx.doi.org/10.1021/acs.joc.7b02257
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