<i>In silico</i> characterization and prediction of thiourea-like neutral bidentate halogen bond catalysts

Hui, Yang; Tan, Choon Hong; Wong, Ming Wah

doi:10.1039/d1ob01092a

Cited by 1 publication

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“…In keeping with our recent efforts toward understanding organic reaction mechanisms and catalysis, [15][16][17][18][19][20][21][22][23][24] we examined the hetero-Michael reactions by means of transition state (TS) modeling using the MN15 [25] DFT method. MN15 is the latest version of Minnesota density functionals, which have been optimized with larger and broader databases and perform well for thermochemistry, barrier heights and noncovalent interactions such as hydrogen bond for organic molecular systems.…”

Section: Computational Methodologymentioning

confidence: 99%

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Hui

Wong

2021

Asian J Org Chem

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The reaction mechanism of six catalyst‐free hetero‐Michael addition reactions in water has been investigated using DFT calculations. Our theoretical results revealed the direct involvement of multiple water molecules in the transition states. The water molecules play a catalytic role in lowering the activation barrier for the three thia‐Michael reactions. Concerted transition state with two bridging water molecules yields the lowest energy barrier. The formation of a hydrogen bonding network via one or more water molecules in the transition state facilitates proton shuttling from the nucleophile to the electrophile. For the aza‐Michael reactions considered, they follow a stepwise mechanism involving the formation of a stable zwitterionic intermediate. In these cases, water influences the reactions via strong (nonspecific) solvent effect and the catalytic role of water is less important for enones that adopt a stable s‐cis conformation. The calculated low reaction barriers (44–83 kJ/mol) of the six studied reactions are in excellent accord with the observed facile hetero‐Michael reactions in water.

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Section: Computational Methodologymentioning

confidence: 99%

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Hui

Wong

2021

Asian J Org Chem

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View full text Add to dashboard Cite

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In silico characterization and prediction of thiourea-like neutral bidentate halogen bond catalysts

Abstract: Preorganization is a common strategy to align halogen bond (XB) donors to form two or more halogen bonds simultaneously. Previous approaches have utilized various non-covalent interactions such as steric interaction,...

Cited by 1 publication

References 67 publications

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

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