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. 2011 Sep 21;133(37):14578-81.
doi: 10.1021/ja206997e. Epub 2011 Aug 25.

Dual catalysis in enantioselective oxidopyrylium-based [5 + 2] cycloadditions

Noah Z Burns  1 , Michael R Witten, Eric N Jacobsen
Affiliations

Dual catalysis in enantioselective oxidopyrylium-based [5 + 2] cycloadditions

Noah Z Burns et al. J Am Chem Soc. .

Abstract

A new method for effecting catalytic enantioselective intramolecular [5 + 2] cycloadditions based on oxidopyrylium intermediates is reported. The dual catalyst system consists of a chiral primary aminothiourea and a second achiral thiourea. Experimental evidence points to a new type of cooperative catalysis with each species being necessary to generate a reactive pyrylium ion pair that undergoes subsequent cycloaddition with high enantioselectivity.

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Figures

Figure 1
Figure 1
(A) Proposed role for thiourea catalysts 10 and 8. Calculated lowest energy cycloaddition transition structures at the B3LYP/6-31G(d) level of theory for (B) 10•pyrylium, and (C) 32•pyrylium.
Scheme 1
Scheme 1
Oxidopyrylium cycloadditions and proposed mode of catalysis
See this image and copyright information in PMC

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