Stereoselective synthesis of a 2,2,5-trisubstituted tetrahydropyran chiron via 1,3- and 1,6-asymmetric induction:: A total synthesis of (-)-malyngolide
Stereoselective synthesis of a 2,2,5-trisubstituted tetrahydropyran chiron via 1,3- and 1,6-asymmetric induction:: A total synthesis of (-)-malyngolide
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DOI：
10.1016/s0040-4020(98)00810-2
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发表时间：
1998-10-22
期刊：
影响因子：
2.1
通讯作者：
Iwata, C
中科院分区：
文献类型：
--
作者：
Maezaki, N;Matsumori, Y;Iwata, C
提出了一种合成手性2，2，5-三取代四氢吡喃的新方法，即通过双环缩醛1的面选择性和基团选择性的缩醛裂解反应，同时引入两个手性中心，从而实现1，3-和16-不对称诱导。结果表明，缩醛断裂的pro-R C-O键和亲核攻击相反的裂解键优先进行。在-100 ° C下，用TiCl 4和三甲基甲硅烷，缩醛分裂的选择性为10：1，亲核的粘性选择性为12：1。该反应已成功地应用于海洋抗生素（-）-马林高内酯的全合成。(C)1998爱思唯尔科技有限公司。保留所有权利。
A new mode of synthesizing chiral 2,2,5-trisubstituted tetrahydropyran is described, in which two chiral centers are simultaneously introduced via facial and group selective nucleophilic acetal cleavage reaction of a bicyclic acetal 1, thereby accomplishing 1,3- and 16-asymmetric induct ion. It is revealed that acetal cleavage of the pro-R C-O bond and nucleophilic attack opposite the cleaved bond proceed preferentially. With TiCl4 and at lyltrimetyl silane at -100 degrees C, the selectivity of acetal fission is 10:1 and that of nucleophilic at tack is 12:1. This reaction is successfully applied to a total synthesis of marine antibiotics, (-)-malyngolide. (C) 1998 Elsevier Science Ltd. All rights reserved.