The palladium-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) has been developed using dialkylbiaryl phosphine ligands. A variety of aryl, heteroaryl, and vinyl halides can be prepared via this method in good to excellent yields.

A method for the hydroxylation of aryl and heteroaryl halides, promoted by a catalyst based on a biarylphosphine ligand tBuBrettPhos (L5) and its corresponding palladium precatalyst (1), is described. The reactions allow the cross-coupling of both potassium and cesium hydroxides with (hetero)aryl halides to afford a variety of phenols and hydroxylated heteroarenes in high to excellent yield.

An efficient, general palladium catalyst for C–O bond-forming reactions of secondary and primary alcohols with a range of aryl halides has been developed. Use of a catalyst based on a single bulky biarylphosphine ligand L4 (RockPhos, soon to be commercially available) has expanded this chemistry to allow the transformation of a variety of heteroaryl halides, and for the first time, allows for t...

We report the Pd-catalyzed α-arylation of α,α-difluoroketones with aryl and heteroaryl bromides and chlorides catalyzed by an air- and moisture-stable palladacyclic complex containing P(t-Bu)Cy2 as ligand. The combination of this Pd-catalyzed arylation and base-induced cleavage of the acyl-aryl C-C bond within the α-aryl-α,α-difluoroketone constitutes a one-pot, two-step procedure to synthesize...

We report the Pd-catalyzed arylation of very hindered α,α,α-trisubstituted primary amines. Kinetics-based mechanistic analysis and rational design have led to the development of two biarylphosphine ligands that allow the transformation to proceed with excellent efficiency. The process was effective in coupling a wide range of functionalized aryl and heteroaryl halides under mild conditions.

Problem solved: an air-stable 2-pyridyl borane that can effectively couple to a wide range of aryl and heteroaryl halides and pseudohalides has evaded the synthesis community for decades. The discovery that Cu(DEA)(2) powerfully enables palladium-mediated cross-couplings with air-stable boronates 1 has finally provided a general solution to this problem. DEA=diethanolamine, DMF=N,N'-dimethylfor...

The synthesis of trifluoromethyl-substituted pyridylboronic acids and pyrazolylboronic esters is described via lithiation-boronation protocols (Schemes 1, 3 and 4). A study of their palladium-catalysed cross-couplings with heteroaryl halides is presented. CF3-substituted aryl/heteroaryl-pyridines are thereby obtained (51-98% yields). Analogous cross-couplings have yielded heteroaryl-3-(trifluor...

Stabilized AlHCl(2)·(THF)(2) hydroaluminates RC≡CH with exceptional chemo-, regio- and stereoselectivity under efficient ZrCl(2)(η-C(5)Me(5))(2) catalysis (2-5 mol%). The resulting vinyl alanes undergo palladium cross-coupling with a wide range of sp(2) electrophiles (aryl, heteroaryl and vinyl halides/pseudohalides) in good to excellent yields.

Various functionalized aryl and heteroaryl aluminum reagents were obtained by performing I-Li or Br-Li exchange reactions with the corresponding unsaturated organic halides in the presence of i-Bu2AlCl. By means of an appropriate catalyst, the resulting new aluminum species were directly acylated, allylated or arylated. 1,4-Michael additions to enones have also been achieved.