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铑催化环状亚胺的亲核烯丙基化反应中烯丙基铑中间体的异构化

The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

作者信息

Hepburn Hamish B, Lam Hon Wai

机构信息

EaStCHEM, School of Chemistry, University of Edinburgh, Joseph Black Building, The King's Buildings, West Mains Road, Edinburgh, EH9 3JJ (UK) http://www.nottingham.ac.uk/∼pczhl; School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).

出版信息

Angew Chem Int Ed Engl. 2014 Oct 20;53(43):11605-10. doi: 10.1002/anie.201407233. Epub 2014 Sep 9.

DOI:10.1002/anie.201407233
PMID:25205604
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4497600/
Abstract

Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes.

摘要

由烯丙基三氟硼酸钾生成的烯丙基铑物种可通过1,4-铑(I)迁移进行异构化,生成更复杂的异构体,然后这些异构体与环状亚胺反应,得到具有多达三个新立体化学元素的产物。使用手性二烯-铑配合物可获得高对映选择性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/874a249ceb1c/anie0053-11605-f9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/0d518477e3a0/anie0053-11605-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/f5416e305089/anie0053-11605-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/68639a5f2840/anie0053-11605-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/20e3de32b5b3/anie0053-11605-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/00cd80d6a006/anie0053-11605-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/bfcdf993ff71/anie0053-11605-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/5bdeedb0813f/anie0053-11605-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/9fb69a86a3f1/anie0053-11605-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/874a249ceb1c/anie0053-11605-f9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/0d518477e3a0/anie0053-11605-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/f5416e305089/anie0053-11605-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/68639a5f2840/anie0053-11605-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/20e3de32b5b3/anie0053-11605-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/00cd80d6a006/anie0053-11605-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/bfcdf993ff71/anie0053-11605-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/5bdeedb0813f/anie0053-11605-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/9fb69a86a3f1/anie0053-11605-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2591/4497600/874a249ceb1c/anie0053-11605-f9.jpg

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