Palladium-catalyzed amination reactions of aryl halides have undergone rapid development in the last 12 years, largely driven by the implementation of new classes of ligands. Biaryl phosphanes have proven to provide especially active catalysts in this context. This Review discusses the application of these catalysts in C-N cross-coupling reactions in the synthesis of heterocycles and pharmaceuticals, in materials science, and in natural product synthesis.

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Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

Catalytic reactions of C–C and C–X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite angles for the selected ligands: dppp, BINAP, dppf, DPEphos and Xantphos. Similarities with hydrocyanation and CO/ethene/MeOH reactions have been highlighted, while rhodium hydroformylation has been mentioned as a contrasting example, in which predictability is high and steric and electronic effects follow smooth trends. In palladium catalysis wide bite angles and bulkiness of the ligands facilitate generally the reductive elimination thus giving more efficient cross coupling catalysis (174 references).

Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions.

Potassium 1-(alkoxy/acyloxy)alkyltrifluoroborates have been synthesized through a copper-catalyzed diboration of aldehydes and subsequent conversion of the resulting potassium 1-(hydroxy)alkyltrifluoroborates. The palladium-catalyzed Suzuki–Miyaura reaction employing the potassium 1-(benzyloxy)alkyltrifluoroborates with aryl and heteroaryl chlorides provides access to protected secondary alcohols in high yields. The β-hydride elimination pathway is avoided through use of the benzyl protecting group, which is proposed to stabilize the diorganopalladium intermediate by coordination of the arene to the metal center. This cross-coupling is stereospecific with complete retention of stereochemistry.

/pdf/stereospecific-cross-coupling-of-secondary-1dnfffsbni.pdf

Stereospecific Cross-Coupling of Secondary Organotrifluoroborates: Potassium 1-(Benzyloxy)alkyltrifluoroborates

Despite the tremendous accomplishments that have been described in the development of palladiumand nickel-catalyzed carbon–carbon bond-forming processes, it is nevertheless true that many signifi cant opportuniti es remain. For example, to date the overwhelming majority of studies have focused on couplings between two sp2-hybridized reacti on sites (e.g., an aryl metal with an aryl halide). As of 2001, there were relati vely few examples of metal-catalyzed coupling reacti ons of alkyl electrophiles. During the past several years, we have pursued the discovery of transiti on metal-based catalysts for coupling acti vated and unacti vated alkyl electrophiles that bear β hydrogens. Our recent eff orts to develop broadly applicable methods, including enanti oselecti ve processes, will be discussed.

Metal‐Catalyzed Cross‐Coupling Reactions

The notion of weak attractive ligand-polymer interactions is introduced, and its potential application, importance, and conceptual links with "cooperative" ligand-substrate interactions are discussed. Synthetic models of weak attractive ligand-polymer interactions are described, in which intramolecular weak C-H...F-C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X-ray diffraction experiments. These C-H...F-C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho-F...H(beta) ligand-polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an "active" ligand and the growing polymer chain is a novel concept in polyolefin catalysis.

Weak attractive ligand-polymer and related interactions in catalysis and reactivity: impact, applications, and modeling.

Syntheses and characterizations of methylpalladium complexes bearing a biphenyl-based bulky phosphine ligand: Weak interactions suggested by NBO and QTAIM analyses

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Syntheses and characterizations of methylpalladium complexes bearing a biphenyl-based bulky phosphine ligand: Weak interactions suggested by NBO and QTAIM analyses