The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation

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-...

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Bibliographic Details
Published in:Organic letters 2021-05, Vol.23 (9), p.3751-3754
Main Authors: De Pascalis, Lucrezia, Yau, Mei-Kwan, Svatunek, Dennis, Tan, Zhuoting, Tekkam, Srinivas, Houk, K. N, Finn, M. G
Format: Article
Language:English
Subjects:
Cycloaddition Reaction
Electrons
Furans - chemistry
Molecular Structure
Sulfhydryl Compounds - chemistry
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Summary: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.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.1c01164