Total synthesis, assignment of absolute stereochemistry, and structural revision of chlorofusin

被引:41
作者
Qian, Wen-Jian [1 ]
Wei, Wan-Guo [1 ]
Zhang, Yong-Xia [1 ]
Yao, Zhu-Jun [1 ]
机构
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Bioorgan & Nat Prod Chem, Shanghai 200032, Peoples R China
关键词
D O I
10.1021/ja072225g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The first total synthesis of chlorofusin was accomplished in a convergent fashion. With all four unambiguous diastereomeric model chromophores as references, the absolute stereochemistry of the chlorofusin chromophore was determined and revised to be (4S,8R,9S) by H-1 NMR studies and asymmetric synthesis. This allows the complete structure of natural chlorofusin to be assigned for the first time. Enantioselective copper-mediated oxidation of 4, mild coupling of azaphilone 2 with the free amine-bearing cyclopeptide 3, and a one-pot three-step protocol for the final spiro-aminal formation were successfully achieved with high efficiency to yield the correct stereochemical product 1a.
引用
收藏
页码:6400 / +
页数:3
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