Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction

Shen, Boming; Chen, Yu; Yu, Peiyuan1

2022-07-01

10.1039/d2qo00682k

Organic Chemistry Frontiers   Impact Factor & Quartile

2052-4129

Density functional theory (DFT) calculations have been performed to investigate the mechanism and origin of the enantio- and regioselectivity of Rh-catalyzed desymmetric [2 + 2 + 2] cycloaddition of enynes with terminal alkynes. The computational results show that the catalytic cycle involves oxidative cyclization of cyclohexadienone alkynes (rate- and enantioselectivity-determining step), alkyne insertion (regioselectivity-determining step), and reductive elimination/catalyst regeneration. Natural population analysis and independent gradient model analysis show that for para-electron donating group-substituted aryl alkynes, the charge distribution of alkynes is the dominant factor controlling the regioselectivity, while for strong electron withdrawing group-substituted aryl alkynes, the regioselectivity is controlled by enhanced pi-pi stacking interactions between the phenyl group of the aromatic alkyne moiety and the phenyl group of the ligand. Distortion/interaction analysis shows that the interaction energy between the rhodacycle complex and the cyclohexadienone alkyne is the determining factor controlling the enantioselectivity.

SCI ; EI

English

Corresponding

SUSTech start-up fund[Y01216143] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Organic

WOS:000827639600001

ROYAL SOC CHEMISTRY

20223012420490

Catalysis ; Computation theory ; Cyclization ; Density functional theory ; Factor analysis ; Hydrocarbons ; Regioselectivity ; Rhodium compounds

Computer Theory, Includes Formal Logic, Automata Theory, Switching Theory, Programming Theory:721.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Probability Theory:922.1 ; Mathematical Statistics:922.2 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Shen, Boming,Chen, Yu,Yu, Peiyuan. Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction[J]. Organic Chemistry Frontiers,2022,9:4625-4632.

Shen, Boming,Chen, Yu,&Yu, Peiyuan.(2022).Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction.Organic Chemistry Frontiers,9,4625-4632.

Shen, Boming,et al."Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction".Organic Chemistry Frontiers 9(2022):4625-4632.