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Enantioselective template-directed [2+2] photocycloadditions of isoquinolones: scope, mechanism and synthetic applications

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<mark>Journal publication date</mark>27/04/2015
<mark>Journal</mark>Chemistry - A European Journal
Issue number18
Volume21
Number of pages7
Pages (from-to)6906–6912
StatePublished
Early online date17/03/15
Original languageEnglish

Abstract

A strategy for the enantioselective [2+2] photocycloaddition of isoquinolones with alkenes is presented, in which the formation of a supramolecular complex between a chiral template and the substrate ensures high enantioface differentiation by shielding one face of the substrate. Fifteen different electron-deficient alkenes and ten different substituted isoquinolones undergo efficient photocycloaddition, yielding the cyclobutane products in excellent yields and with outstanding regio-, diastereo- and enantioselectivities (up to 99 % ee). The mechanism of the reaction is investigated by means of triplet sensitization/quenching and radical clock experiments, the results of which are consistent with the involvement of a triplet excited state and a 1,4-biradical intermediate. The variety of functionalized cyclobutanes obtained using this approach can be further increased by straightforward synthetic transformations of the photoadducts, allowing rapid access to libraries of compounds for various applications.