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手性镍催化的通过可逆烯基镍 E/Z 异构化实现的分子内烯丙基烯基化反应。

Enantioselective Nickel-Catalyzed Intramolecular Allylic Alkenylations Enabled by Reversible Alkenylnickel E/Z Isomerization.

机构信息

The GSK Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU, UK.

School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.

出版信息

Angew Chem Int Ed Engl. 2017 Jul 3;56(28):8216-8220. doi: 10.1002/anie.201703380. Epub 2017 Jun 12.

DOI:10.1002/anie.201703380
PMID:28544752
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5499723/
Abstract

Enantioselective nickel-catalyzed arylative cyclizations of substrates containing a Z-allylic phosphate tethered to an alkyne are described. These reactions give multisubstituted chiral aza- and carbocycles, and are initiated by the addition of an arylboronic acid to the alkyne, followed by cyclization of the resulting alkenylnickel species onto the allylic phosphate. The reversible E/Z isomerization of the alkenylnickel species is essential for the success of the reactions.

摘要

描述了含有 Z-烯丙基膦酸酯键联炔烃的底物的对映选择性镍催化芳基环化反应。这些反应生成多取代的手性氮杂环和碳环,由芳基硼酸与炔烃加成引发,随后得到的烯基镍物种在烯丙基膦酸酯上进行环化。烯基镍物种的可逆 E/Z 异构化对于反应的成功至关重要。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/1a89e9909630/ANIE-56-8216-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/4f2fbb4a8add/ANIE-56-8216-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/f73f2c2868c1/ANIE-56-8216-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/27f4b4c764b1/ANIE-56-8216-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/1a89e9909630/ANIE-56-8216-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/4f2fbb4a8add/ANIE-56-8216-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/f73f2c2868c1/ANIE-56-8216-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/27f4b4c764b1/ANIE-56-8216-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f9d/5499723/1a89e9909630/ANIE-56-8216-g004.jpg

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