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Azanorbornadienes as Thiol-Reactive Cleavable Linkers.

ABSTRACT: Azanorbornadienes (ZNDs), prepared from pyrroles, undergo Michael reaction with thiols followed by retro-Diels-Alder (rDA) cleavage to release the starting pyrrole and a thiomaleate. Somewhat less reactive in this regard than furan-derived oxanorbornadienes, ZNDs have an additional point of variability at the pyrrole nitrogen center. Sulfonylated ZNDs were far more stable toward rDA cleavage than acylated analogues. tert-Butoxycarbonyl examples were much less reactive with thiols, rendering the rDA step slower than the initial conjugate addition.

SUBMITTER: De Pascalis L

PROVIDER: S-EPMC9019847 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Azanorbornadienes as Thiol-Reactive Cleavable Linkers.

De Pascalis Lucrezia L Tekkam Srinivas S Finn M G MG

Organic letters 20200805 16

Azanorbornadienes (ZNDs), prepared from pyrroles, undergo Michael reaction with thiols followed by retro-Diels-Alder (rDA) cleavage to release the starting pyrrole and a thiomaleate. Somewhat less reactive in this regard than furan-derived oxanorbornadienes, ZNDs have an additional point of variability at the pyrrole nitrogen center. Sulfonylated ZNDs were far more stable toward rDA cleavage than acylated analogues. <i>tert</i>-Butoxycarbonyl examples were much less reactive with thiols, renderi ...[more]

PMID: 32806178

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