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RESEARCH ARTICLE
Contents Vol 68(11)

Enantioselective Photochemical Rearrangements of Spirooxindole Epoxides Catalyzed by a Chiral Bifunctional Xanthone

Mark M. Maturi A , Alexander Pöthig A and Thorsten Bach A B
+ Author Affiliations
- Author Affiliations

A Department Chemie and Catalysis Research Center (CRC), Technische Universität München, D-85747 Garching, Germany.

B Corresponding author. Email: thorsten.bach@ch.tum.de

Australian Journal of Chemistry 68(11) 1682-1692 https://doi.org/10.1071/CH15280
Submitted: 15 May 2015  Accepted: 12 June 2015   Published: 17 July 2015

Abstract

The title compounds were shown to undergo an enantioselective photochemical rearrangement to 3-acylindolin-2-ones (16–33 % ee). A xanthone, which is tethered via an anellated oxazole to a chiral 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-one scaffold, efficiently catalyzed this reaction at λ 366 nm, presumably by triplet sensitization. The observed enantioselectivity can be explained by hydrogen bonding of the oxindole substrate and the putative 1,3-diradical intermediate to the lactam part of the catalyst. Although one substrate enantiomer is processed with minor preference over the other, it was shown that the reaction is not stereospecific. Rather, the main reason for the observed selectivity is the enantioselective migration step.


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