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Photomediated ring contraction of saturated heterocycles.

ABSTRACT: Saturated heterocycles are found in numerous therapeutics and bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light-mediated ring contraction of α-acylated saturated heterocycles. This unconventional transformation is orthogonal to traditional ring contractions, challenging the paradigm for diversification of heterocycles including piperidine, morpholine, thiane, tetrahydropyran, and tetrahydroisoquinoline derivatives. The success of this Norrish type II variant rests on reactivity differences between photoreactive ketone groups in specific chemical environments. This strategy was applied to late-stage remodeling of pharmaceutical derivatives, peptides, and sugars.

SUBMITTER: Jurczyk J

PROVIDER: S-EPMC8627180 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Photomediated ring contraction of saturated heterocycles.

Jurczyk Justin J Lux Michaelyn C MC Adpressa Donovon D Kim Sojung F SF Lam Yu-Hong YH Yeung Charles S CS Sarpong Richmond R

Science (New York, N.Y.) 20210812 6558

Saturated heterocycles are found in numerous therapeutics and bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light-mediated ring contraction of α-acylated saturated heterocycles. This unconventional trans ...[more]

PMID: 34385352

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