𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Theoretical study of the reaction mechanism and solvent effect on the regioselectivity of 1,3-dipolar cycloaddition reaction between azide and acetylene derivatives

✍ Scribed by Xi-Bo Li; Qin-Hua Song

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
109 KB
Volume
18
Category
Article
ISSN
1042-7163

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

The reaction mechanism and solvent‐dependant regioselectivity of 1,3‐dipolar cycloaddition reactions between azide and acetylene derivatives have been studied using computational methods. The two possible reaction transition states were located. Geometry and NBO analysis found that the reactions take place along a synchronous and concerted mechanism for TS1 and an asynchronous and less concerted mechanism for TS2. SCRF analysis found that TS2 is more sensitive to the polarity of solvent. In less polar solvent such as CCl~4~, the difference of activation barriers of the two transition states is small. However, when the reactions were conducted in water, the activation barriers for TS2 increase which leads to the observed regioselectivity. Β© 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:203–207, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20236

πŸ“œ SIMILAR VOLUMES

Theoretical study on the mechanism of th
Theoretical study on the mechanism of the cycloaddition reaction between stannylene and ethylene or formaldehyde
✍ Xiu-Hui Lu; Li-Min Zhai; Ayi-Xnan Wang πŸ“‚ Article πŸ“… 2010 πŸ› John Wiley and Sons 🌐 English βš– 323 KB πŸ‘ 2 views

## Abstract The mechanism of the cycloaddition reaction of singlet stannylene and ethylene or formaldehyde has been studied by using density functional theory. The geometrical parameters, harmonic vibrational frequencies and energies of stationary points for potential energy surface are calculated

Cycloaddition of Benzonitrile Oxide to A
Cycloaddition of Benzonitrile Oxide to Acetonitrile, Propyne and Propene βˆ’ A Comparative Theoretical Study of the Reaction Mechanism and Regioselectivity
✍ Vincenzo Vullo; TimothyΒ N. Danks; Gabriele Wagner πŸ“‚ Article πŸ“… 2004 πŸ› John Wiley and Sons 🌐 English βš– 157 KB πŸ‘ 1 views

## Abstract Quantum chemical calculations (MP2/6‐31G\* and B3LYP/6‐31G\*) were used to compare the reactivity, regioselectivity and orbital involvement of the reaction of benzonitrile oxide with the dipolarophiles acetonitrile, propyne and propene. All reactions are thermodynamically favoured. The