jo7b02816_si_004.cif (637.4 kB)
Ligand-Effect in Gold(I)-Catalyzed Rautenstrauch Rearrangement: Regio- and Stereoselective Synthesis of Bicyclo[3.2.1]octa-3,6-dienes through Cyclodimerization of 1‑Ethynyl-2-propenyl Esters
dataset
posted on 2018-01-12, 00:00 authored by Jidong Zhao, Shuang Yang, Xin Xie, Xiangdong Li, Yuanhong LiuGold(I) complexes
bearing sterically demanding phosphine ligands
such as tBuXphos catalyze the cascade
Rautenstrauch rearrangement/[4 + 3] cycloaddition of 1-ethynyl-2-propenyl
esters. The reaction provides an efficient and straightforward route
to bicyclo[3.2.1]octa-3,6-dienes with high regio- and stereoselectivity.
The formation of the [4 + 3] cycloadducts likely proceeds through
the cycloaddition of a gold(I) carbenoid/gold-stabilized allyl cation
intermediate with cyclopentadiene arising from Rautenstrauch rearrangement.