The asymmetric total synthesis of (+)-waihoensene, which has a cis-fused [6,5,5,5] tetracyclic core bearing an angular triquinane, a cis-fused six-membered ring, and four contiguous quaternary car-bon atoms, was achieved through a sequence of chemical reac-tions in a stereochemically well-defined manner. The total synthe-sis features: 1) Cu-catalyzed asymmetric conjugated 1,4-addition; 2) diastereoselective Conia-ene reaction; 3) diastereoselective intramolecular Pauson-Khand reaction; 4) Ni-catalyzed diastere-oselective conjugated 1,4-addition; and 5) radical-initiated intra-molecular hydrogen atom transfer (HAT). Control experiments and density functional theory calculations support the proposed HAT process.

中文翻译：

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(+)-Waihoensene的不对称全合成

(+)-waihoensene 的不对称全合成，其具有顺式稠合 [6,5,5,5] 四环核心，带有角三喹烷、顺式稠合六元环和四个连续的季碳原子, 是通过一系列化学反应以立体化学上明确定义的方式实现的。总合成特点： 1）Cu催化不对称共轭1,4-加成；2) 非对映选择性的 Conia-ene 反应；3)非对映选择性分子内Pauson-Khand反应；4) Ni催化的非对映选择性共轭1,4-加成；5)自由基引发的分子内氢原子转移(HAT)。控制实验和密度泛函理论计算支持提议的 HAT 过程。