The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation

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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Veröffentlicht in:Organic letters 2021-05, Vol.23 (9), p.3751-3754
Hauptverfasser: De Pascalis, Lucrezia, Yau, Mei-Kwan, Svatunek, Dennis, Tan, Zhuoting, Tekkam, Srinivas, Houk, K. N, Finn, M. G
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Sprache:eng
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Cycloaddition Reaction
Electrons
Furans - chemistry
Molecular Structure
Sulfhydryl Compounds - chemistry
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container_end_page 3754
container_issue 9
container_start_page 3751
container_title Organic letters
container_volume 23
creator De Pascalis, Lucrezia
Yau, Mei-Kwan
Svatunek, Dennis
Tan, Zhuoting
Tekkam, Srinivas
Houk, K. N
Finn, M. G
description 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.
doi_str_mv 10.1021/acs.orglett.1c01164
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subjects Cycloaddition Reaction
Electrons
Furans - chemistry
Molecular Structure
Sulfhydryl Compounds - chemistry
title The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation
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