[Angew. Chem. Int. Ed.] Prof. Yandong Zhang published a paper entitled “Total Synthesis of Aplydactone by a Conformationally Controlled C−H Functionalization”

Publish Date:2017-6-7     Visited1153Times    bsp;  

Title: Total Synthesis of Aplydactone by a Conformationally Controlled C−H Functionalization

Author: Chenguang Liu, Renzhi Chen, Yang Shen, Zhanhao Liang, Yuhui Hua, Prof. Dr. Yandong Zhang*

A concise, protecting-group-free total synthesis of the unusual brominated sesquiterpene aplydactone is described. Our synthesis features a [2+2] photocycloaddition, a Wolff ring contraction, an unusual remote C−H functionalization to establish the highly strained tetracyclic core, and a hydrogen-atom transfer (HAT) reaction to access the bromine-containing stereocenter. A finely tuned conformation of the α-diazoketone precursor is the key for the success of the late-stage transannular C−H insertion to deliver a bridged six-membered ring and a quaternary stereocenter (C6) between two quaternary carbon atoms (C1 and C7).


Full Link: http://onlinelibrary.wiley.com/doi/10.1002/anie.201703803/full