Ph2P(BH3)Li: from ditopicity to dual reactivity.

A multinuclear NMR study shows that the deprotonation of diphenylphosphine-borane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph(2)P(BH(3))Li of which Li(+) is connected to the hydrides on the boron and two THF molecules rather than to the phosphorus. This entity behaves as both a phosphination and a reducing agent, depending on the kinetic or thermodynamic control imposed to the reaction medium. Density functional theory computations show that H(2)P(BH(3))Li exhibits a ditopic character (the lithium cation can be in the vicinity of the hydride or of the phosphorus). It explains its dual reactivity (H- or P-addition), both routes going through somewhat similar six-membered transition states with low activation barriers.

Copper-catalyzed synthesis of alkynylphosphine derivatives: unprecedented use of nucleophilic phosphorus compounds.

A new and smooth approach towards alkynylphosphine derivatives is described. It relies on the unprecedented catalytic coupling of secondary phosphine boranes with alkynyl bromides using the CuI/1,10-phenanthroline couple.

Palladium-catalyzed C-P coupling reactions between vinyl triflates and phosphine-boranes: efficient access to vinylphosphine-boranes.

Vinylphosphine-borane complexes are easily synthesized by palladium-catalyzed C-P cross-coupling of vinyl triflates with secondary phosphine-boranes. This method allows the synthesis of phosphine derivatives not always easily accessible by other approaches. The vinylphosphine derivatives are purified by chromatography on silica gel. The versatility of the method is proved by using various triflates and diaryl-, dialkyl- and alkylarylphosphine-borane precursors. Chiral enantiopure phosphine-boranes are synthesized from chiral triflates.

Pallado-catalysed hydrophosphination of alkynes: access to enantio-enriched P-stereogenic vinyl phosphine-boranes.

Preliminary results dealing with the synthesis of non-racemic P-stereogenic vinylphosphine-boranes by hydrophosphination of alkynes in the presence of a chiral catalyst are reported.

Regioselective uncatalysed hydrophosphination of alkenes: a facile route to P-alkylated phosphine derivatives.

The synthesis of alkylarylphosphines is easily carried out by hydrophosphination of unactivated alkenes under mild thermal activation; gram scale amounts of products can be prepared by this simple methodology.

Transition-metal-containing chiral bidentate ligands for enantioselective catalysis: non-metallocene architectural units come of age.

Structural and electronic properties associated with donor ligands that contain 'spectator' transition-metal fragments are analyzed. The current status of such non-ferrocenyl chiral bidentate ligands is reviewed from the standpoint of synthesis, applications in metal-catalyzed enantioselective reactions, and future directions.

New approaches to high-activity transition-metal catalysts for carbon-carbon bond forming reactions. Rhenium-containing phosphorus donor ligands for palladium-catalyzed Suzuki cross-couplings.

The rhenium complexes (eta 5-C5H5)Re(NO)(PPh3)((CH2)nPR2:) (n/R = 0/Ph, 0/t-Bu, 0/Me, 1/Ph, 1/t-Bu), which contain electron-rich and sterically congested phosphido moieties, give active catalysts for the title reaction; typical conditions (toluene, 60-100 degrees C): aryl bromide (1.0 equiv.), PhB(OH)2 (1.5 equiv.), K3PO4 (2.0 equiv.), Pd(OAc)2 (1 mol%), and a Re(CH2)nPR2: species or a 1:2 [Re(CH2)nPR2H]+X-/t-BuOK mixture (4 mol% rhenium).