Intramolecular photoreactions of (5S)-5-Oxymethyl-2(5H)-furanones as a tool for the stereoselective generation of diverse polycyclic scaffolds
Lejeune, Guillaume (Universitat Autònoma de Barcelona. Departament de Química)
Font i Cierco, Josep (Universitat Autònoma de Barcelona. Departament de Química)
Parella Coll, Teodor (Universitat Autònoma de Barcelona. Servei de Ressonància Magnètica Nuclear)
Alibes, Ramón (Universitat Autònoma de Barcelona. Departament de Química)
Figueredo Galimany, Marta (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2015
Abstract:	The photoactivated evolution of a series of enantiomerically pure 5-oxymethyl-2(5H)-furanones has been investigated. The observed intramolecular photoreactions have proven to be a straightforward entry to diverse and stereochemically rich fragment-molecules, most of which contain the privileged tetrahydropyran (THP) scaffold. The formation of the THP involves a 1,5-hydrogen atom transfer process, leading to a diradical intermediate that recombines to form a new σ C-C bond. These reactions take place under both sensitized and nonsensitized conditions, and they are highly stereoselective. When the substrate contains an allyl residue, the intramolecular [2 + 2] cycloaddition leading to cyclobutanes competes advantageously. When the substrate contains a THP residue, the cyclization involves the concomitant formation of [6,6]-spiroketals with nonanomeric relationships.
Grants:	Ministerio de Economía y Competitividad CTQ2013-41161-R Ministerio de Ciencia e Innovación CTQ2012-32436 Ministerio de Ciencia e Innovación CTQ2010-15380
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Cyclization ; Irradiation ; Ketones ; Lactones ; Mixtures
Published in:	Journal of organic chemistry, Vol. 80, issue 19 (Oct. 2015) , p. 9437-9445, ISSN 1520-6904

DOI: 10.1021/acs.joc.5b01354

Postprint 27 p, 768.2 KB

The record appears in these collections:
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