Organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover
Taiga Kodo,
Kazunori Nagao () and
Hirohisa Ohmiya ()
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Taiga Kodo: Kanazawa University, Kakuma-machi
Kazunori Nagao: Kanazawa University, Kakuma-machi
Hirohisa Ohmiya: Kyoto University, Gokasho
Nature Communications, 2022, vol. 13, issue 1, 1-7
Abstract:
Abstract Over the past century, significant progress in semipinacol rearrangement involving 1,2-migration of α-hydroxy carbocations has been made in the areas of catalysis and total synthesis of natural products. To access the α-hydroxy carbocation intermediate, conventional acid-mediated or electrochemical approaches have been employed. However, the photochemical semipinacol rearrangement has been underdeveloped. Herein, we report the organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover (RPC). A phenothiazine-based organophotoredox catalyst facilitates the generation of an α-hydroxy non-benzylic alkyl radical followed by oxidation to the corresponding carbocation, which can be exploited to undergo the semipinacol rearrangement. As a result, the photochemical approach enables decarboxylative semipinacol rearrangement of β-hydroxycarboxylic acid derivatives and alkylative semipinacol type rearrangement of allyl alcohols with carbon electrophiles, producing α-quaternary or α-tertiary carbonyls bearing sp3-rich scaffolds.
Date: 2022
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-30395-4
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DOI: 10.1038/s41467-022-30395-4
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