American Chemical Society
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

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posted on 2018-01-12, 00:00 authored by Jidong Zhao, Shuang Yang, Xin Xie, Xiangdong Li, Yuanhong Liu
Gold­(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.