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.
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 pi 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.
Sakata
Ken
K
Faculty of Pharmaceutical Sciences, Hoshi University, Ebara, Shinagawa-ku, Tokyo, 142-8501, Japan. sakata@hoshi.ac.jp
Miyake
Yoshihiro
Y
Nishibayashi
Yoshiaki
Y
D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D020005:Propanols / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry; D013816:Thermodynamics
D000475:Alkenes; D000480:Alkynes; D007659:Ketones; D020005:Propanols; D013455:Sulfur; D002244:Carbon; D012428:Ruthenium; C028255:propargyl alcohol