Enantioselective Intramolecular ortho Photocycloaddition Reactions of 2-Acetonaphthones

Peng Yan, Simone Stegbauer, Qinqin Wu, Elena Kolodzeiski, Christopher J. Stein, Ping Lu, Thorsten Bach

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4 Scopus citations

Abstract

2-Acetonaphthones, which bear an alkenyl group tethered to its C1 carbon atom via an oxygen atom, were found to undergo an enantioselective intramolecular ortho photocycloaddition reaction. A chiral oxazaborolidine Lewis acid leads to a bathochromic absorption shift of the substrate and enables an efficient enantioface differentiation. Visible light irradiation (λ=450 nm) triggers the reaction which is tolerant of various groups at almost any position except carbon atom C8 (16 examples, 53–99 % yield, 80–97 % ee). Consecutive reactions were explored including a sensitized rearrangement to tetrahydrobiphenylenes, which occurred with full retention of configuration. Evidence was collected that the catalytic photocycloaddition occurs via triplet intermediates, and the binding mode of the acetonaphthone to the chiral Lewis acid was elucidated by DFT calculations.

Original languageEnglish
Article numbere202318126
JournalAngewandte Chemie International Edition in English
Volume63
Issue number13
DOIs
StatePublished - 22 Mar 2024

Keywords

  • Cycloaddition
  • Lewis Acid
  • enantioselectivity
  • photochemistry
  • rearrangements

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