Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol

Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol

Iwasaki, K.; Wan, K. K.; Oppedisano, A.; Crossley, S. W. M.; Shenvi, R. A. J. Am. Chem. Soc. 2014, ASAP.

DOI: 10.1021/ja412342g

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.

 

Hydrogenation of Alkenes – addition of H-H (H2) to the π-bond of alkenes to afford an alkane. The reaction must be catalyzed by metals such as Pd, Pt, Rh, and Ni.

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The catalytic hydrogenation that take place at the “less hindered” side of a reactant are common in organic chemistry and are examples of steric effects on reactivity.  Dissolving metal reduction provides a means to achieve thermodynamic control and can reduce only conjugated or electron-poor alkenes at low temperature, but with extremely low functional group tolerance.  Shenvi and coworkers has developed new method for the thermodynamic hydrogenation of alkenes (Mn(dmp)3, PhSiH3, TBHP, i-PrOH, RT).

ryanshenvi

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