APPLICATIONS OF AN ASYMMETRIC [2 + 2]-PHOTOCYCLOADDITION - TOTAL SYNTHESIS OF (-)-ECHINOSPORIN - CONSTRUCTION OF AN ADVANCED 11-DEOXYPROSTAGLANDIN INTERMEDIATE

被引:37
作者
SMITH, AB [1 ]
SULIKOWSKI, GA [1 ]
SULIKOWSKI, MM [1 ]
FUJIMOTO, K [1 ]
机构
[1] UNIV PENN,RES STRUCT MATTER LAB,PHILADELPHIA,PA 19104
关键词
D O I
10.1021/ja00033a033
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The first total synthesis of the novel antitumor metabolite (-)-echinosporin (1) has been achieved. Asymmetric [2 + 21-photocycloaddition of dihydrofuran acetonide (+)-8 to 2-cyclopentenone (7) constituted the cornerstone of the synthetic strategy. Mitsunobu lactonization of hemiacetal acid 43 generated the tricyclic framework of 1, which embodies a strain energy of ca. 17 kcal/mol as estimated by MNDO calculations. The successful synthetic venture permitted assignment of the absolute configuration of echinosporin. Construction of the Corey 11-deoxyprostaglandin intermediate (+)-49 further demonstrated the utility of (+)-8 as a chiral building block.
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页码:2567 / 2576
页数:10
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