Asymmetric Total Synthesis of (+)-Waihoensene
Asymmetric Total Synthesis of (+)-Waihoensene
复制标题
( )-Waihoensene 的不对称全合成
DOI：
10.1021/jacs.0c02143
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发表时间：
2020-04-08
影响因子：
15
通讯作者：
Yang, Zhen
中科院分区：
文献类型：
--
作者：
Qu, Yongzheng;Wang, Zheyuan;Yang, Zhen
通过一系列立体化学定义明确的化学反应，实现了（+）-waihoenestrine的不对称全合成，该化合物具有一个带有角型三醌的顺式稠合[6，5，5，5]四环核，一个顺式稠合六元环和四个连续的季碳原子。全合成的特点如下：（1）铜催化的不对称共轭1，4-加成;（2）非对映选择性Conia-烯型反应;（3）非对映选择性分子内Pauson-Khand反应;（4）镍催化的非对映选择性共轭1，4-加成;和（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所提出的HAT过程。
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 carbon atoms, was achieved through a sequence of chemical reactions in a stereochemically well-defined manner. The total synthesis features the following: (1) Cu-catalyzed asymmetric conjugated 1,4-addition; (2) diastereoselective Conia-ene type reaction; (3) diastereoselective intramolecular Pauson-Khand reaction; (4) Ni-catalyzed diastereoselective conjugated 1,4-addition; and (5) radical-initiated intramolecular hydrogen atom transfer (HAT). Control experiments and density functional theory calculations support the proposed HAT process.