Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
J Org Chem. 2016 Aug 5;81(15):6757-65. doi: 10.1021/acs.joc.6b00608. Epub 2016 Jul 8.
Reported here is a formal synthesis of gracilamine using Rh(I)-catalyzed [3 + 2 + 1] reaction of yne-VCP (±)-4 and CO. The key reaction gave the cycloadduct (±)-trans-3 with the A-B-C core structure of gracilamine. This advanced intermediate was further transformed to Gao's intermediate (±)-2 via regular transformations to realize the formal synthesis of gracilamine. The present strategy was used to accomplish the asymmetric formal synthesis of gracilamine using chiral substrate (+)-4.
本文报道了使用 Rh(I) 催化的炔-VCP（±）-4 和 CO 的 [3 + 2 + 1] 反应对 graceamine 进行的正式合成。关键反应得到了具有 graceamine 的 A-B-C 核心结构的环加成物（±）-trans-3。该高级中间体通过常规转化进一步转化为高中间体（±）-2，从而实现 graceamine 的正式合成。本策略用于使用手性底物 (+)-4 完成 graceamine 的不对称正式合成。
