Intermolecular Crossed [2 + 2] Cycloaddition Promoted by Visible-Light Triplet Photosensitization: Expedient Access to Polysubstituted 2-Oxaspiro[3.3]heptanes

Philip R.D. Murray, Willem M.M. Bussink, Geraint H.M. Davies, Farid W. Van Der Mei, Alyssa H. Antropow, Jacob T. Edwards, Laura Akullian D'Agostino, J. Michael Ellis, Lawrence G. Hamann, Fedor Romanov-Michailidis, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

Abstract

This paper describes an intermolecular cross-selective [2 + 2] photocycloaddition reaction of exocyclic arylidene oxetanes, azetidines, and cyclobutanes with simple electron-deficient alkenes. The reaction takes place under mild conditions using a commercially available Ir(III) photosensitizer upon blue light irradiation. This transformation provides access to a range of polysubstituted 2-oxaspiro[3.3]heptane, 2-azaspiro[3.3]heptane, and spiro[3.3]heptane motifs, which are of prime interest in medicinal chemistry as gem-dimethyl and carbonyl bioisosteres. A variety of further transformations of the initial cycloadducts are demonstrated to highlight the versatility of the products and enable selective access to either of a syn- or an anti-diastereoisomer through kinetic or thermodynamic epimerization, respectively. Mechanistic experiments and DFT calculations suggest that this reaction proceeds through a sensitized energy transfer pathway.

Original languageEnglish (US)
Pages (from-to)4055-4063
Number of pages9
JournalJournal of the American Chemical Society
Volume143
Issue number10
DOIs
StatePublished - Mar 17 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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