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- Title
Organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover.
- Authors
Kodo, Taiga; Nagao, Kazunori; Ohmiya, Hirohisa
- 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. Although electrochemical semipinacol rearrangements have been reported, a complementary photochemical route has yet to be developed. Here the authors report an organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover.
- Subjects
ALLYL alcohol; CARBOCATIONS; ALKYL radicals; ACID derivatives; NATURAL products; HYDROXYCINNAMIC acids
- Publication
Nature Communications, 2022, Vol 13, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-022-30395-4