A DFT Study on the Reaction Pathways for Carbon-Carbon Bond‐Forming Reactions between Propargylic Alcohols and Alkenes or Ketones Catalyzed by Thiolate‐Bridged Diruthenium Complexes

Abstract

The reaction pathways of two types of the carboncarbon bond-forming reactions catalyzed by thiolate-bridged diruthenium complexes have been investigated by density-functional-theory calculations. It is clarified that both carboncarbon bond-forming reactions proceed through a ruthenium–allenylidene complex as a common reactive intermediate. The attack of π electrons on propene or the vinyl alcohol on the ruthenium–allenylidene complex is the first step of the reaction pathways. The reaction pathways are different after the attack of nucleophiles on the ruthenium–alkynyl complex. In the reaction with propene, the carboncarbon bond-forming reaction proceeds through a stepwise process, whereas in the reaction with vinyl alcohol, it proceeds through a concerted process. The interactions between the ruthenium–allenylidene complex and propene or vinyl alcohol have been investigated by applying a simple way of looking at orbital interactions.