Alleman Cécile, Gadais Charlène, Legentil Laurent, Porée François-Hugues
Université Rennes, Faculté de Pharmacie, CNRS ISCR UMR 6226, F-35000 Rennes, France.
Université Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR - UMR 6226, F-35000 Rennes, France.
Beilstein J Org Chem. 2023 Mar 3;19:245-281. doi: 10.3762/bjoc.19.23. eCollection 2023.
Terpene compounds probably represent the most diversified class of secondary metabolites. Some classes of terpenes, mainly diterpenes (C20) and sesterterpenes (C25) and to a lesser extent sesquiterpenes (C15), share a common bicyclo[3.6.0]undecane core which is characterized by the presence of a cyclooctane ring fused to a cyclopentane ring, i.e., a [5-8] bicyclic ring system. This review focuses on the different strategies elaborated to construct this [5-8] bicyclic ring system and their application in the total synthesis of terpenes over the last two decades. The overall approaches involve the construction of the 8-membered ring from an appropriate cyclopentane precursor. The proposed strategies include metathesis, Nozaki-Hiyama-Kishi (NHK) cyclization, Pd-mediated cyclization, radical cyclization, Pauson-Khand reaction, Lewis acid-promoted cyclization, rearrangement, cycloaddition and biocatalysis.
萜类化合物可能是次生代谢产物中最多样化的一类。某些萜类，主要是二萜（C20）和倍半萜（C25），以及程度较轻的倍半萜（C15），具有共同的双环[3.6.0]十一烷核心，其特征是存在一个与环戊烷环稠合的环辛烷环，即[5-8]双环系统。本综述重点关注在过去二十年中为构建这种[5-8]双环系统而设计的不同策略及其在萜类全合成中的应用。总体方法包括从合适的环戊烷前体构建八元环。提出的策略包括复分解反应、野依-日向-岸环化反应（NHK环化反应）、钯介导的环化反应、自由基环化反应、鲍森-坎德反应、路易斯酸促进的环化反应、重排反应、环加成反应和生物催化反应。
