A Study on the Photoreaction of 2(5H)-Furanones with Substituted Acetylenes: Evidence for a Mechanistic Reformulation

Ramon Flores, Josep Font, Ramon Alibés, Marta Figueredo

Research output: Contribution to journalArticleResearchpeer-review

1 Citation (Scopus)

Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The photoreaction of 2(5H)-furanones with alkynes has been investigated. The complexity of this process is evidenced by the variety of isolated products, which have allowed disclosing interesting mechanistic aspects. When the reaction is performed in acetonitrile under direct excitation, in addition to the primary [2+2] cycloadducts, products derived from an 1,3-acyl shift rearrangement are also formed. For unsymmetrical alkynes, the rearrangement of the head-to-tail primary adducts produces new regioisomers and, when the starting furanone is chiral, this rearrangement inverts the relative anti/syn geometry of the primary cycloadducts. In the reactions performed in acetone under photosensitized conditions, rearranged products were never detected, supporting that the 1,3-acyl shift takes place from the singlet excited state S 1 of the β,γ-unsaturated lactone. When bis(trimethylsilyl)acetylene is used as the alkyne partner, the major photoproducts are monocyclic bis(trimethylsilyl)lactones.
Original languageEnglish
Pages (from-to)3835-3845
JournalChemistry - A European Journal
Volume22
Issue number11
DOIs
Publication statusPublished - 7 Mar 2016

Keywords

  • 2(5H)-furanones
  • alkynes
  • photoreactions
  • regioselectivity
  • stereoselectivity

Fingerprint

Dive into the research topics of 'A Study on the Photoreaction of 2(5H)-Furanones with Substituted Acetylenes: Evidence for a Mechanistic Reformulation'. Together they form a unique fingerprint.

Cite this