A study on the photoreaction of 2(5H)-furanones with substituted acetylenes : evidence for a mechanistic reformulation
Flores Pons, Ramon (Universitat Autònoma de Barcelona. Departament de Química)
Font i Cierco, Josep (Universitat Autònoma de Barcelona. Departament de Química)
Alibes, Ramón (Universitat Autònoma de Barcelona. Departament de Química)
Figueredo Galimany, Marta (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2016
Abstract:	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.
Grants:	Ministerio de Economía y Competitividad CTQ2013-41161-R Ministerio de Ciencia e Innovación CTQ2010-15380
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Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	2(5H)-furanones ; Alkynes ; Photoreactions ; Regioselectivity ; Stereoselectivity
Published in:	Chemistry (Weinheim), Vol. 22, issue 11 (March 2016) , p. 3835-3845, ISSN 1521-3765

DOI: 10.1002/chem.201503888

Postprint 14 p, 903.2 KB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Synthesis of Bioactive Organic Compounds and Functional Materials (SynOrgFUN)
Articles > Research articles
Articles > Published articles