Formal Synthesis of Gracilamine Using Rh(I)-Catalyzed [3+2+1] Cycloaddition of 1-Yne-Vinylcyclopropanes and CO
Formal Synthesis of Gracilamine Using Rh(I)-Catalyzed [3+2+1] Cycloaddition of 1-Yne-Vinylcyclopropanes and CO
复制标题
Rh(I) 催化正式合成 Gracilamine [3 2 1] 1-Yne-乙烯基环丙烷与 CO 的环加成反应
DOI：
10.1021/acs.joc.6b00608
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发表时间：
2016-08-05
影响因子：
3.6
通讯作者：
Yu, Zhi-Xiang
中科院分区：
文献类型：
--
作者：
Bose, Sritama;Yang, Jun;Yu, Zhi-Xiang
本文报道了在Rh（I）催化下，炔-VCP（+/-）-4与CO的[3 + 2 + 1]反应，合成了具有A-B-C核结构的（+/-）-trans-3环加成物。该高级中间体通过常规转化进一步转化为Gao的中间体（+/-）-2，实现了Gracilamine的形式化合成。采用该方法以手性底物（+）-4为底物，实现了对乙酰氨基苯甲酸的不对称缩甲醛合成。
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.