Unconventional exo selectivity in thermal normal-electron-demand Diels-Alder reactions.

ABSTRACT: The Diels-Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels-Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric

SUBMITTER: Ho GM 

PROVIDER: S-EPMC5059706 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature