Asymmetric Total Synthesis of Caribenol A via an Intramolecular Diels-Alder Reaction

作者:Han, Jing-Chun; Liu, Lian-Zhu; Chang, Yuan-Yuan; Yue, Guo-Zong; Guo, Jie; Zhou, Li-Yan; Li, Chuang-Chuang*; Yang, Zhen
来源:Journal of Organic Chemistry, 2013, 78(11): 5492-5504.
DOI:10.1021/jo4006156

摘要

A total synthesis of the caribenol A (1), a novel natural product with an intriguing tetracyclic framework, has been achieved. The synthesis features an intramolecular Diels-Alder (IMDA) reaction for the facile construction of the tricyclic [5-7-6] skeleton of caribenol A (1) and a biomimetic oxidation reaction for the formation of the 2-hydroxyfuran-2(5H)-one motif of caribenol A (1) as key steps. This synthetic approach also reveals that the sp(2) carbon at C(2) in substrate 8 is a critical factor for the formation of the tricyclic [5-7-6] skeleton in 7.