and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

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Are alkyne reductions chemo-, regio-, and stereoselective enough to provide pure (Z)-olefins in polyfunctionalized bioactive molecules?

The nonclassical ruthenium hydride pincer complex [Ru(PNP)(H)(2)(H(2))] 1 (PNP = 1,3-bis(di-tert-butyl-phosphinomethyl)pyridine) catalyzes the anti-Markovnikov addition of pinacolborane to terminal alkynes yielding Z-vinylboronates at mild conditions. The complex [Ru(PNP)(H)(2)(HBpin)] 2 (HBpin = pinacolborane), which was identified at the end of the reaction and prepared independently, is proposed as the direct precursor to the catalytic cycle involving rearrangement of coordinated alkyne to Z-vinylidene as a key step for the apparent trans-hydroboration.

Ruthenium Catalyzed Hydroboration of Terminal Alkynes to Z-Vinylboronates

Tetrahedron report number 25 : Ketone enolates: regiospecific preparation and synthetic uses

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.

Catalytic hydrogenation. VI. Reaction of sodium borohydride with nickel salts in ethanol solution. P-2 Nickel, a highly convenient, new, selective hydrogenation catalyst with great sensitivity to substrate structure

Saline hydrides and superbases in organic reactions. VII. Potassium hydride, highly active new hydride reagent. Reactivity, applications, and techniques in organic and organometallic reactions

Catalytic hydrogenation. V. Reaction of sodium borohydride with aqueous nickel salts. P-1 nickel boride, a convenient, highly active nickel hydrogenation catalyst

Selective hydroboration of double bonds in the presence of triple bonds by 9-borabicyclo[3.3.1]nonane. A new route to acetylenic organoboranes and alcohols

Saline hydrides and superbases in organic reactions. II. Facile reaction of potassium hydride with ketones. Rapid, quantitative formation of potassium enolates from ketones via kaliation

Charles Allan Brown

Papers

Catalytic hydrogenation. VI. Reaction of sodium borohydride with nickel salts in ethanol solution. P-2 Nickel, a highly convenient, new, selective hydrogenation catalyst with great sensitivity to substrate structure

Saline hydrides and superbases in organic reactions. VII. Potassium hydride, highly active new hydride reagent. Reactivity, applications, and techniques in organic and organometallic reactions

Catalytic hydrogenation. V. Reaction of sodium borohydride with aqueous nickel salts. P-1 nickel boride, a convenient, highly active nickel hydrogenation catalyst

Selective hydroboration of double bonds in the presence of triple bonds by 9-borabicyclo[3.3.1]nonane. A new route to acetylenic organoboranes and alcohols

Saline hydrides and superbases in organic reactions. II. Facile reaction of potassium hydride with ketones. Rapid, quantitative formation of potassium enolates from ketones via kaliation