Alcohols as Alkylating Agents: Photoredox-Catalyzed Conjugate Alkylation via In Situ Deoxygenation.

Autor: Wang JZ; Merck Center for Catalysis at Princeton University, Washington Road, Princeton, NJ 08544, USA., Sakai HA; Merck Center for Catalysis at Princeton University, Washington Road, Princeton, NJ 08544, USA., MacMillan DWC; Merck Center for Catalysis at Princeton University, Washington Road, Princeton, NJ 08544, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Aug 26; Vol. 61 (35), pp. e202207150. Date of Electronic Publication: 2022 Jul 19.
DOI: 10.1002/anie.202207150
Abstrakt: The rapid exploration of sp 3 -enriched chemical space is facilitated by fragment-coupling technologies that utilize simple and abundant alkyl precursors, among which alcohols are a highly desirable, commercially accessible, and synthetically versatile class of substrate. Herein, we describe an operationally convenient, N-heterocyclic carbene (NHC)-mediated deoxygenative Giese-type addition of alcohol-derived alkyl radicals to electron-deficient alkenes under mild photocatalytic conditions. The fragment coupling accommodates a broad range of primary, secondary, and tertiary alcohol partners, as well as structurally varied Michael acceptors containing traditionally reactive sites, such as electrophilic or oxidizable moieties. We demonstrate the late-stage diversification of densely functionalized molecular architectures, including drugs and biomolecules, and we further telescope our protocol with metallaphotoredox cross-coupling for step-economic access to sp 3 -rich complexity.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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