2) Gold-Catalyzed Reaction of ortho-Alkynylarylaldehydes with Conjugated Dienes: An Efficient Access to Highly Strained Tetracyclic Bridgehead Olefins

Ziping Cao,* Hongbo Zhu, Xin Meng, Laijin Tian, Xuejun Sun, Guang Chen, and Jinmao You*

Chem. Eur. J. 2016, 22, 9125–9129.

School of Chemistry and Chemical Engineering, Qufu Normal University

http://onlinelibrary.wiley.com/doi/10.1002/chem.201601430/abstract

An unprecedented access to strained tetracyclic bridgehead alkenes by reaction of easily accessible ortho-alkynylarylaldehydes with conjugated dienes is described. The process involves a chemo- and stereo-selective, gold-catalyzed, tandem intermolecular [3+2] cycloaddition/Prins-type ring closing reaction that allows generating structural complexity in a straightforward manner. This approach for the preparation of anti- Bredt compounds is synthetically superior to those previously reported: the procedure is easy to implement, operates under mild experimental conditions, is efficient, and exhibits a good substrate scope.