Molecular Dynamics of the Davies Ambimodal C–H Functionalization/Cope Rearrangement Reaction DOI

Yaling Zhang,

Chaoqin Cao,

Yuanbin She

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

The mechanism of the dirhodium-catalyzed combined C–H functionalization/Cope rearrangement (CH/Cope) reaction discovered by Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from previously showed that there is a post-transition state bifurcation leading to direct CH also CH/Cope product. While this work was in preparation, Tantillo Ess independently reported quantum mechanical studies on dirhodium-tetracarboxylate-catalyzed diazoester insertion reactions 1,3-cyclohexadiene 1,4-cyclohexadiene, respectively. cited "dynamic mismatching" explain origins low yield products some experiments; explained product selectivity perspective TS vibrational modes their synchronization occurs at entropic intermediates. We report trajectories for carbene 1-methylcyclohexene afford both products. After passing through transition involves mostly hydrogen transfer, momentum drives toward

Language: Английский

Hexafluoroisopropanol Solvent Effects on Enantioselectivity of Dirhodium Tetracarboxylate-Catalyzed Cyclopropanation DOI Creative Commons
Turki M. Alturaifi,

Kristin Shimabukuro,

Jack C. Sharland

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

In recent years, additives that modulate both reactivity and selectivity in rhodium-catalyzed reactions of aryldiazoacetates have become increasingly prominent. 1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) has been shown to a profound effect on rhodium carbene selectivity, especially enabling cyclopropanation the presence various nucleophilic poisons. HFIP also variable influence enantioselectivity catalyzed by chiral dirhodium tetracarboxylates, this study examines fundamental properties carbene/HFIP system through experimentation, density functional theory (DFT), molecular dynamics (MD) simulations. These studies revealed C4-symmetric bowl-shaped catalysts, which previously considered be relatively rigid, experience far greater flexibility hydrogen bonding media, resulting distortion catalysts. explain why even though majority catalysts drop HFIP, some such as Rh2(TCPTAD)4, lead switch enantioselectivity, whereas others, Rh2(NTTL)4, considerably enhanced enantioselectivity.

Language: Английский

Citations

0
Molecular Dynamics of the Davies Ambimodal C–H Functionalization/Cope Rearrangement Reaction DOI

Yaling Zhang,

Chaoqin Cao,

Yuanbin She

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

The mechanism of the dirhodium-catalyzed combined C–H functionalization/Cope rearrangement (CH/Cope) reaction discovered by Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from previously showed that there is a post-transition state bifurcation leading to direct CH also CH/Cope product. While this work was in preparation, Tantillo Ess independently reported quantum mechanical studies on dirhodium-tetracarboxylate-catalyzed diazoester insertion reactions 1,3-cyclohexadiene 1,4-cyclohexadiene, respectively. cited "dynamic mismatching" explain origins low yield products some experiments; explained product selectivity perspective TS vibrational modes their synchronization occurs at entropic intermediates. We report trajectories for carbene 1-methylcyclohexene afford both products. After passing through transition involves mostly hydrogen transfer, momentum drives toward

Language: Английский

Citations

1