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新型实用的双环乙内酰脲硫代内酯立体选择性合成，作为生产（+）-生物素的关键中间体。

Novel practical stereoselective synthesis of a bicyclic hydantoino-thiolactone as the key intermediate for production of (+)-biotin.

作者信息

Shu Lei, Yang Zhi-Wei, Cao Ren-Xu, Qiu Xiao-Xia, Ni Feng, Shi Xiao-Xin

机构信息

Engineering Research Center of Pharmaceutical Process Chemistry of the Ministry of Education, School of Pharmacy, East China University of Science and Technology 130 Mei-Long Road Shanghai 200237 P. R. China

Shanghai Shyndec Pharmaceutical Co., Ltd. 378 Jian-Lu Road Shanghai 201203 P. R. China

出版信息

RSC Adv. 2023 Sep 4;13(37):26160-26168. doi: 10.1039/d3ra04721k. eCollection 2023 Aug 29.

DOI:10.1039/d3ra04721k
PMID:37671003
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10475979/
Abstract

Bicyclic hydantoinothiolactone (1), as the key intermediate for production of (+)-biotin, has been efficiently and high-stereoselectively synthesized from the cheap starting material l-cystine nine steps in 44% overall yield. In this new practical synthesis, there are two characteristic steps worthy of note. One step is TMSOTf-catalyzed efficient cyanation of (3,7a)-6-benzyl-5-oxo-3-phenyltetrahydro-1,3-imidazo[1,5-]thiazol-7-yl acetate, the other step is DBU-catalyzed rapid isomerization of -isomer to -isomer of the bicyclic hydantoinothiolactone.

摘要

双环乙内酰脲硫代内酯（1）作为生产（+）-生物素的关键中间体，已从廉价起始原料L-胱氨酸出发，经九步反应以44%的总收率高效且高立体选择性地合成出来。在这种新的实用合成方法中，有两个值得注意的特征步骤。一步是三甲基甲磺酸钪催化（3,7a）-6-苄基-5-氧代-3-苯基四氢-1,3-咪唑并[1,5-a]噻唑-7-基乙酸酯的高效氰化反应，另一步是1,8-二氮杂双环[5.4.0]十一碳-7-烯催化双环乙内酰脲硫代内酯的α-异构体快速异构化为β-异构体反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/e97546c88217/d3ra04721k-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/20971774539d/d3ra04721k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/b13da1408d5c/d3ra04721k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/8c66b73ee850/d3ra04721k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/1971be2a9ca5/d3ra04721k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/016f2012c744/d3ra04721k-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/d7b394fd0808/d3ra04721k-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/55d80d00941d/d3ra04721k-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/45ebbd564a84/d3ra04721k-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/4e734481fd52/d3ra04721k-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/e97546c88217/d3ra04721k-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/20971774539d/d3ra04721k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/b13da1408d5c/d3ra04721k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/8c66b73ee850/d3ra04721k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/1971be2a9ca5/d3ra04721k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/016f2012c744/d3ra04721k-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/d7b394fd0808/d3ra04721k-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/55d80d00941d/d3ra04721k-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/45ebbd564a84/d3ra04721k-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/4e734481fd52/d3ra04721k-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f7ac/10475979/e97546c88217/d3ra04721k-f8.jpg

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