Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes

Abstract

A detailed computational study of the intramolecular Alder-ene reaction of different 1,6-dienes at M06-2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile-geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM-distortion interaction model) reveals that the cis-selectivity observed for unactivated reagents is related with high stabilizing orbital interaction and lower strain energy, consequence of an early transition structure. On the other hand, the presence of activating groups increases the asynchronicity of the transition structures and reduces the activation barrier due to more stabilizing orbital and electrostatic interactions, favoring trans-selectivity.

Experimental and theoretical elucidation of SPAAC kinetics for strained alkyne-containing cycloparaphenylenes

“…We next implemented the distortion/interaction model to understand the origin of the reactivity differences of the [n+1] CPPs towards benzyl azide. The distortion/interaction model 30,31 is an energy-decomposition scheme that has been used extensively to understand the origin of unimolecular [32][33][34][35] and bimolecular [36][37][38][39][40] reactions. The distortion/interaction model dissects activation energies into distortion and interaction energies.…”

Cyclization reactions of 1,6-dienes and 1,6-enynes by dual cobalt photocatalysis

“…Cycloisomerization of 1,6-dienes 19 and reductive cyclization of 1,6-enynes 20 provide an effective means for the preparation of five-membered cyclic compounds. The reactions have been realized by cobalt catalysis via the intermediacy of [Co III ]–H species (Fig.…”