Oxetane Synthesis through the Paternò-Büchi Reaction

Abstract

Abstract:The Paternò-Büchi reaction is a photochemical reaction between a carbonyl compound and an alkene to give the corresponding oxetane. In this review the mechanism of the reaction is discussed. On this basis the described use in the reaction with electron rich alkenes (enolethers, enol esters, enol silyl ethers, enanines, heterocyclic compounds has been reported. The stereochemical behavior of the reaction is particularly stressed. We pointed out the reported applications of this reaction to the synthesis of naturally occuring compounds.

Indications of 5′ to 3′ Interbase Electron Transfer as the First Step of Pyrimidine Dimer Formation Probed by a Dinucleotide Analog

“…Given the similar structures between thietane and oxetane, it is reasonable that the thymidine photoreaction may as well proceed via an oxetane intermediate to form 6-4PP. However, although oxetane intermediates via the Paternò-Büchi reaction are relatively common in organic photochemistry, [38] the lifetime of the oxetane intermediate generated during the 6-4PP formation is estimated to be ~ 4 milliseconds in the dinucleotide TpT photoreaction. [39] Our calculations indicate that oxetane rearrangement to 6-4PP may involve protonation of the basic O4b position.…”

Photochemical Approaches to the Bilobalide Core

“…[23][24][25] A succinimide as a C 4 building block would allow the sequential attachment of both the furan moiety (i.e., the second C 4 unit, required to construct ring D) and a 4,4dimethylpentane-2-one chain (precursor for ring B) to the same carbon atom in an arylation/Michael-addition sequence. [23][24][25] A succinimide as a C 4 building block would allow the sequential attachment of both the furan moiety (i.e., the second C 4 unit, required to construct ring D) and a 4,4dimethylpentane-2-one chain (precursor for ring B) to the same carbon atom in an arylation/Michael-addition sequence.…”

Photokatalyse mit sichtbarem Licht: Welche Bedeutung hat sie für die organische Synthese?

“…Formale [2+ +2]-Cycloadditionen, die von weichen Lewis-Säuren katalysiert werden, die Kohlenstoff-Kohlenstoff-p-Bindungen aktivieren kçnnen, wurden kürzlich von der Gruppe um Chirik verçffentlicht. [236] Pionierarbeiten von Pandey [237] und Yoon [202,204,238] zeigten, dass [2+ +2]-Cycloadditionen zwischen zwei elektronenarmen Alkenen durch sichtbares Licht [239] mit einem Photoredoxkatalysator realisiert werden kçnnen. Thermische [2+ +2]-Cycloadditionen über Charge-Transfer-Komplexe mit anschließendem Elektronentransfer zwischen elektronenreichen und elektronenarmen Alkenen, insbesondere Tetracyanethylen als außergewçhnlich starker Elektronenakzeptor, sind ebenfalls mçglich.…”