- Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor
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There are few examples of catalytic transfer hydrogenations of simple alkenes and alkynes that use water as a stoichiometric H or D atom donor. We have found that diboron reagents efficiently mediate the transfer of H or D atoms from water directly onto unsaturated C-C bonds using a palladium catalyst. This reaction is conducted on a broad variety of alkenes and alkynes at ambient temperature, and boric acid is the sole byproduct. Mechanistic experiments suggest that this reaction is made possible by a hydrogen atom transfer from water that generates a Pd-hydride intermediate. Importantly, complete deuterium incorporation from stoichiometric D2O has also been achieved.
- Cummings, Steven P.,Le, Thanh-Ngoc,Fernandez, Gilberto E.,Quiambao, Lorenzo G.,Stokes, Benjamin J.
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supporting information
p. 6107 - 6110
(2016/06/09)
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- Simple, chemoselective hydrogenation with thermodynamic stereocontrol
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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.
- Iwasaki, Kotaro,Wan, Kanny K.,Oppedisano, Alberto,Crossley, Steven W. M.,Shenvi, Ryan A.
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supporting information
p. 1300 - 1303
(2014/02/14)
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- Directing Effects in Homogeneous Hydrogenation with PF6
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The presence of a ligating group, e.g., OH, CO2Me, C=O, or OMe, on an olefinic substrate is shown to direct the attack of the hydrogenation catalyst PF6/H2/CH2Cl2 from the face of the molecule containing the directing group.Isomerization is a minor side reaction in the cases studied.The origin of this effect is discussed and a model intermediate isolated.
- Crabtree, Robert H.,Davis, Mark W.
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p. 2655 - 2661
(2007/10/02)
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- APPLICATION OF 1H NMR AND 13C NMR FOR ESTABLISHING THE SPATIAL STRUCTURE OF STEREOISOMERIC o- AND p-MENTHANE, o- AND p-MENTHENES, AND ISOPROPYLCYCLOHEXANE.
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An attempt to establish the spatial structure of stereoisomeric o- and p-menthanes, 8-o- and 8-p-menthenes, and isopropylcyclohexane on the basis of an analysis of the **1H NMR and **1**3C NMR spectra is described.
- Bazyl'chik,Samitov,Ryabushkina
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p. 543 - 548
(2007/10/02)
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