Exploring the chemistry of E/Z configuration in gold-catalyzed domino cyclization: Insights on the stereoselectivity

• Published in: Molecular catalysis Vol. 519; p. 112154
• Main Authors: Li, Yunhe, Zhang, Jie, Zhao, Xiang, Wang, Youliang
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2022
• Subjects: Configuration preference; DFT; E/Z selectivity; Gold catalysis; Substitutions; Gold catalysis; E/Z selectivity; DFT; Configuration preference; Substitutions
• ISSN: 2468-8231; 2468-8231
• DOI: 10.1016/j.mcat.2022.112154

•E/Z configuration selectivity controlled by both catalyst and substrate.•Conformation match between the dihedral angle and the Gibbs energy barrier.•Energetic discrimination is controlled by substitutions effects.•Correction between the ΔΔG and the degree of slippage of the C−N interaction. The mechanism and origins of Z/E configuration selectivity of gold-catalyzed domino cyclization were computationally investigated. The influence of the nature of the different substitutions present in the gold catalyst on the Z/E selectivity is investigated. The Z/E configuration selectivity involved in two processes: initial spirocyclization and hydroamination. The spirocyclization step represents the rate-determining step. Computational results indicated a strong energetic preference for Z configuration based on transition states analysis, which provided hints for further developments of new templates. This quantitatively analyzed model would be helpful in understanding and tuning the conformation preference in sequential cyclization to construct chiral center. Graphical Abstract [Display omitted] .