Remote Steric and Electronic Effects of N-Heterocyclic Carbene Ligands on Alkene Reactivity and Regioselectivity toward Hydrocupration Reactions: The Role of Expanded-Ring N-Heterocyclic Carbenes DOI
Aqeel A. Hussein, Azhar Ariffin

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 13009 - 13021

Published: Aug. 31, 2023

The remote groups in N-heterocyclic carbene (NHC) ligands have a significant influence on metal-catalyzed reactions. We examine how bulkiness, electronic groups, and expanded-ring NHCs (ER-NHCs) alkene reactivity regioselectivity toward hydrocupration using density functional theory calculations. impact of steric bulkiness the Cu–H insertion rate is analyzed, revealing strong correlation between substituent constant ratio, where bulky group increases due to reduced effects transition state (TS). properties examined catalysts (with R2 = CPh3, CHPh2, CH2Ph, CH3, H) their corresponding TSs are found be modulated greatly by substitution ring size NHC ligand. Enhanced enhances nucleophilic moiety. smaller barrier compared that hindrance. Furthermore, ER-NHC exploration indicates with over five-membered rings significantly negative reaction rate. Finally, highly (R2 CPh3), anti-Markovnikov preference attributed high interaction energy improved properties. Overall, our findings here provide valuable insights for development more effective catalyst

Language: Английский

Remote Steric and Electronic Effects of N-Heterocyclic Carbene Ligands on Alkene Reactivity and Regioselectivity toward Hydrocupration Reactions: The Role of Expanded-Ring N-Heterocyclic Carbenes DOI
Aqeel A. Hussein, Azhar Ariffin

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 13009 - 13021

Published: Aug. 31, 2023

The remote groups in N-heterocyclic carbene (NHC) ligands have a significant influence on metal-catalyzed reactions. We examine how bulkiness, electronic groups, and expanded-ring NHCs (ER-NHCs) alkene reactivity regioselectivity toward hydrocupration using density functional theory calculations. impact of steric bulkiness the Cu–H insertion rate is analyzed, revealing strong correlation between substituent constant ratio, where bulky group increases due to reduced effects transition state (TS). properties examined catalysts (with R2 = CPh3, CHPh2, CH2Ph, CH3, H) their corresponding TSs are found be modulated greatly by substitution ring size NHC ligand. Enhanced enhances nucleophilic moiety. smaller barrier compared that hindrance. Furthermore, ER-NHC exploration indicates with over five-membered rings significantly negative reaction rate. Finally, highly (R2 CPh3), anti-Markovnikov preference attributed high interaction energy improved properties. Overall, our findings here provide valuable insights for development more effective catalyst

Language: Английский

Citations

0