The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation
Lucrezia De Pascalis, Mei‐Kwan Yau, Dennis Svatunek, Zhuoting Tan, Srinivas Tekkam, K. N. Houk, M. G. Finn
Abstract
Oxanorbornadienes (ONDs) undergo facile Michael addition with thiols and then fragment by a retro-Diels-Alder (rDA) reaction, a unique two-step sequence among electrophilic cleavable linkages. The rDA reaction rate was explored as a function of the furan structure, with substituents at the 2- and 5-positions found to be the most influential and the fragmentation rate to be inversely correlated with electron-withdrawing ability. Density functional theory calculations provided an excellent correlation with the experimentally measured OND rDA rates.
Topics & Concepts
ChemistryFragmentation (computing)FuranElectrophileThiolStereochemistryDensity functional theoryComputational chemistryOrganic chemistryCatalysisComputer scienceOperating systemOrganic Chemistry Cycloaddition ReactionsSulfur-Based Synthesis TechniquesRadical Photochemical Reactions