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氨基甲酸酯导向的苄位锂化反应用于非对映选择性和对映选择性合成二芳基醚轴手性异构体。

Carbamate-directed benzylic lithiation for the diastereo- and enantioselective synthesis of diaryl ether atropisomers.

机构信息

School of Chemistry, University of Manchester, Oxford Rd., Manchester M13 9PL, UK.

出版信息

Beilstein J Org Chem. 2011;7:1327-33. doi: 10.3762/bjoc.7.156. Epub 2011 Sep 26.

DOI:10.3762/bjoc.7.156
PMID:22043243
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3201046/
Abstract

Diaryl ethers carrying carbamoyloxymethyl groups may be desymmetrised enantio- and diastereoselectively by the use of the sec-BuLi-(-)-sparteine complex in diethyl ether. Enantioselective deprotonation of one of the two benzylic positions leads to atropisomeric products with ca. 80:20 e.r.; an electrophilic quench typically provides functionalised atropisomeric diastereoisomers in up to 97:3 d.r.

摘要

带有氨基甲酰氧甲基的二芳基醚可以通过使用叔丁基锂-(-)-辛可宁复合物在二乙醚中对映选择性和非对映选择性地去对称化。对两个苄位之一的对映选择性去质子化导致约 80:20 的对映体过量的非对映异构体；亲电猝灭通常以高达 97:3 的 d.r.提供官能化的非对映异构体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/1ac7cea29ab1/Beilstein_J_Org_Chem-07-1327-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/bea7eb36d070/Beilstein_J_Org_Chem-07-1327-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/1a1014443beb/Beilstein_J_Org_Chem-07-1327-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/ef74a43b183d/Beilstein_J_Org_Chem-07-1327-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/2ed96b348e42/Beilstein_J_Org_Chem-07-1327-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/3be89d732ef1/Beilstein_J_Org_Chem-07-1327-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/03b03736e16e/Beilstein_J_Org_Chem-07-1327-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/1ac7cea29ab1/Beilstein_J_Org_Chem-07-1327-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/bea7eb36d070/Beilstein_J_Org_Chem-07-1327-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/1a1014443beb/Beilstein_J_Org_Chem-07-1327-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/ef74a43b183d/Beilstein_J_Org_Chem-07-1327-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/2ed96b348e42/Beilstein_J_Org_Chem-07-1327-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/3be89d732ef1/Beilstein_J_Org_Chem-07-1327-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/03b03736e16e/Beilstein_J_Org_Chem-07-1327-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c44/3201046/1ac7cea29ab1/Beilstein_J_Org_Chem-07-1327-g008.jpg

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