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. 2008 Nov 12;130(45):14960-1.
doi: 10.1021/ja806979b. Epub 2008 Oct 21.

Asymmetric synthesis of bicyclo[4.3.1]decadienes and bicyclo[3.3.2]decadienes via [6 + 3] trimethylenemethane cycloaddition with tropones

Barry M Trost  1 , Patrick J McDougall, Olaf Hartmann, Peter T Wathen
Affiliations

Asymmetric synthesis of bicyclo[4.3.1]decadienes and bicyclo[3.3.2]decadienes via [6 + 3] trimethylenemethane cycloaddition with tropones

Barry M Trost et al. J Am Chem Soc. .

Abstract

The cyanosubstituted trimethylenemethane donor undergoes palladium-catalyzed [6 + 3] cycloaddition with a variety of tropones to yield bicyclo[4.3.1]decadienes in excellent regio-, diastereo-, and enantioselectivity. Products of the Pd-TMM [6 + 3] cycloaddition participate in a thermal [3,3] sigmatropic rearrangement to yield bicyclo[3.3.2]decadienes in good yield.

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Figures

Figure 1
Figure 1
Phosphoramidite Ligand Screena a Reactions performed at 0.1 M in toluene with 5 mol% Pd(dba)2, 10 mol% ligand, 1.0 equiv. 3a, 1.6 equiv. 2, 0-4 °C for 15 h. ee determined by chiral HPLC.
Scheme 1
Scheme 1
Pd-TMM [3+2] and [6+3] Cycloadditions
See this image and copyright information in PMC

References

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    1. An intramolecular asymmetric [6+4] cycloaddition to a tropone (40% ee) has been reported: Rigby JH, Fleming M. Tetrahedron Lett. 2002;43:8643.

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