Addition of water and ammonia to the carbon–carbon double bond of acyclic alkenes and strained bicyclic dienes; a computational study

Abstract

Calculations have been carried out on the hydration and amination of alkenes to give alcohols and amines respectively. This density functional theory computational study shows both reactions to be exothermic. The enthalpies are in the −7 to −16 kcal mol −1 range for acyclic alkenes. Computationally, unsubstituted alkenes, or those substituted with electron donor groups, undergo hydration and amination reactions more readily than electron deficient alkenes. Formation of branched isomers is favored over linear ones, which correlates with the preference for Markovnikov addition. Strained bicyclic dienes show enthalpies that range between −11 and −33 kcal mol −1. The higher values for the dienes reflects the release of ring strain in the addition reaction. For norbornadiene dicarboxylic acids, addition to the unsubstituted double bond is favored. For the hydration reaction, addition to a double bond substituted with hydroxymethyl groups is favored over one substituted with carboxylic acid groups. Ruthenium(II) and palladium(0) TPPTS complexes have been used for the hydration of 1-octene to 1-octanol.