Density Functional Theory Study of the Metal-Catalyzed Cycloaddition of Indolyl-Allenes: Possible Reaction Pathways, Stereoselectivity, and Regioselectivity

The mechanism, stereoselectivity, and regioselectivity in the Au- and Pt-catalyzed cycloadditions of indolyl-allenes were explored by density functional theory (DFT). Three different catalytic systems, PtCl2, [JohnPhosAu]+, and [IPrAu]+, were selected as model catalysts. The DFT calculations revealed that the [JohnPhosAu]+ catalyst features a reaction pathway completely different from those of the PtCl2 and [IPrAu]+ catalytic systems. The PtCl2-catalyzed process preferably begins with cis coordination and leads to the R configuration products via cis [3+2] cycloaddition. Furthermore, the stereoselectivity of the indolyl-allenes is mainly controlled by the interaction energy. In the [JohnPhosAu]+-catalyzed process, a relatively lower distortion energy, observed for the new reaction pathway proposed by our DFT calculations, enables the formation of the S configuration products through the trans [3+2] cycloaddition step that becomes the principal pathway. On the other hand, the electronic properties of the substituent in the substrate have a combined influence on the selective formation of different products in the [IPrAu]+-catalyzed reactions. The obtained theoretical data explain well the formation of different products when using these three distinct catalytic systems and provide a theoretical foundation for selecting an optimal catalyst in such cycloaddition reactions of indolyl-allenes. © 2020 American Chemical Society.

Fang R.1, 2 , Feng Z.2 , Kirillov A.M. 3, 4 , Yang L. 1, 2
American Chemical Society
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  • 1 College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an, 710021, China
  • 2 State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China
  • 3 Centro de Quĺmica Estrutural, Complexo i, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon, 1049-001, Portugal
  • 4 Peoples' Friendship University of Russia, RUDN University, 6 Miklukho-Maklaya st., Moscow, 117198, Russian Federation
Ключевые слова
Catalysis; Catalysts; Chlorine compounds; Cycloaddition; Density functional theory; Electronic properties; Gold compounds; Hydrocarbons; Platinum compounds; Praseodymium compounds; Regioselectivity; Stereoselectivity; Substrates; Catalyzed reactions; Cycloaddition reaction; Density functional theory studies; Distortion energy; Interaction energies; Selective formation; Theoretical foundations; [3+2]-cycloaddition; Iodine compounds
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