Istituto di Chimica Biomolecolare del CNR, Traversa La Crucca 3, I-07040 Li Punti, Sassari, Italy.
Org Biomol Chem. 2010 Apr 7;8(7):1725-30. doi: 10.1039/b924721a. Epub 2010 Feb 9.
An efficient, stereocontrolled synthesis of (6S,7S,8S,8aR)-6,7,8-trihydroxyindolizidine (alias 1-deoxy-7,8-di-epi-castanospermine) (14) has been developed, which exploits an asymmetric vinylogous Mukaiyama aldol reaction (VMAR) between N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsilyloxy)pyrrole (1) and 2,3-O-isopropylidene-D-glyceraldehyde (2) to construct the initial pyrrolidine building block 3, and an ene-ene ring closing metathesis reaction (RCM) (9 to 10) to install the indolizidine skeleton. The synthetic sequence was 13 steps, proceeding in 19.5% overall yield. The configurational and conformational structure of 14 was ascertained unambiguously and confronted to previously published assignments of rac-14 and ent-14.
已开发出一种高效、立体选择性合成（6S,7S,8S,8aR）-6,7,8-三羟基吲哚里西啶（别名 1-脱氧-7,8-二-表-苦参碱）（14）的方法，该方法利用不对称乙烯基 Mukaiyama 醛缩反应（VMAR），使 N-（叔丁氧羰基）-2-（叔丁基二甲基甲硅烷基氧基）吡咯（1）和 2,3-O-亚异丙基-D-甘油醛（2）反应，构建初始吡咯烷砌块 3，并通过烯-烯环封闭复分解反应（RCM）（9 到 10）安装吲哚里西啶骨架。该合成序列有 13 步，总收率为 19.5%。14 的构型和构象结构已被明确确定，并与 rac-14 和 ent-14 的先前发表的分配进行了对比。
