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The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation

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journal contribution
posted on 14.04.2021, 14:38 by Lucrezia De Pascalis, Mei-Kwan Yau, Dennis Svatunek, Zhuoting Tan, Srinivas Tekkam, K. N. Houk, M. G. Finn
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.