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. 2014 Jan 29;136(4):1300-3.
doi: 10.1021/ja412342g. Epub 2014 Jan 15.

Simple, chemoselective hydrogenation with thermodynamic stereocontrol

Kotaro Iwasaki  1 , Kanny K Wan, Alberto Oppedisano, Steven W M Crossley, Ryan A Shenvi
Affiliations

Simple, chemoselective hydrogenation with thermodynamic stereocontrol

Kotaro Iwasaki et al. J Am Chem Soc. .

Abstract

Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure.

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Figures

Figure 1
Figure 1
Kinetic versus thermodynamic hydrogenation. (a) Example of stereodivergent hydrogenation; (b) examples where kinetic hydrogenation yields the incorrect stereoisomer; (c) poor chemoselectivity of dissolving metal reduction might be circumvented by HAT hydrogenation.
Scheme 1
Scheme 1. Examples of Divergent Stereocontrol
41 contained 16% of the 1,9-isomer. 43 contained 26% of the 1,6-isomer.
Scheme 2
Scheme 2. Observed Reactivity Trends and Cyclizations
See this image and copyright information in PMC

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