Pd-Catalyzed Dearomative [3 + 2] Cycloaddition of 3-Nitroindoles with 2-Vinylcyclopropane-1,1-dicarboxylates

Authors

Yi Sing Gee, University of WollongongFollow
Daniel Rivinoja, University of WollongongFollow
Steven M. Wales, University of WollongongFollow
Michael G. Gardiner, University of Tasmania
Jack Ryan, CSIRO ManufacturingFollow
Christopher J. T Hyland, University of WollongongFollow

RIS ID

118196

Publication Details

Gee, Y., Rivinoja, D. J., Wales, S., Gardiner, M. G., Ryan, J. H. & Hyland, C. J. T. (2017). Pd-Catalyzed Dearomative [3 + 2] Cycloaddition of 3-Nitroindoles with 2-Vinylcyclopropane-1,1-dicarboxylates. Journal of Organic Chemistry, 82 (24), 13517-13529.

Abstract

A trans-diastereoselective Pd-catalyzed dearomative [3 + 2] cycloaddition between vinylcyclopropane dicarboxylates and 3-nitroindoles has been developed. The reaction provides densely functionalized cyclopenta [b] indolines with versatile vinyl and nitro-groups. The addition of a halide additive was found to be critical for the diastereoselectivity of the reaction, which is proposed to be a result of a rapid π-σ-π interconversion between the intermediates allowing for Curtin-Hammett control. A switch in diastereoselectivity to afford products with the vinyl and nitro groups cis to each other is observed with a 4-substituted 3-nitroindole.