New catalysts for Suzuki-Miyaura coupling reactions of heteroatom-substituted heteroaryl chlorides.

The new air-stable PdCl2[PR2(Ph-R')]2 complexes, readily prepared from commercial reagents, exhibit unique efficiency as catalysts for the Suzuki-Miyaura coupling reactions of a variety of heteroatom-substituted heteroaryl chlorides with a diverse range of aryl/heteroaryl boronic acids. The coupling reactions catalyzed by the new complexes exhibit high product yields (88-99%) and high catalyst turnover numbers (up to 10,000 TON).

New air-stable catalysts for general and efficient suzuki-miyaura cross-coupling reactions of heteroaryl chlorides.

[reaction: see text] New air-stable PdCl(2){P(t)Bu(2)(p-R-Ph)}(2) (R = H, NMe(2), CF(3),) complexes represent simple, general, and efficient catalysts for the Suzuki-Miyaura cross-coupling reactions of aryl halides including five-membered heteroaryl halides and heteroatom-substituted six-membered heteroaryl chlorides with a diverse range of arylboronic acids. High product yields (89-99% isolated yields) and turn-over-numbers (10,000 TON) are observed.

Productive chloroarene C-cl bond activation: palladium/phosphine-catalyzed methods for oxidation of alcohols and hydrodechlorination of chloroarenes.

The palladium/phosphine-catalyzed productive chloroarene C-Cl bond activation provides general, efficient, and functional group friendly methods for the selective oxidation of alcohols and the hydrodechlorination of chloroarenes.

Productive utilization of chlorobenzene: palladium-catalyzed selective oxidation of alcohols.

[reaction: see text] The palladium/ligand-catalyzed activation of chlorobenzene provides a general, efficient, and functional group friendly method for the selective oxidation of alcohols to carbonyl compounds.

Palladium/P,O-Ligand-Catalyzed Suzuki Cross-Coupling Reactions of Arylboronic Acids and Aryl Chlorides. Isolation and Structural Characterization of (P,O)-Pd(dba) Complex.

The phenyl backbone-derived P,O-ligands 1 and 2 were investigated for their utility as ligands in palladium/ligand-catalyzed Suzuki reactions. The 2-(2'-dicyclohexylphosphinophenyl)-2-methyl-1,3-dioxolane (ligand 1) in combination with Pd(dba)(2) affords an efficient catalyst for general Suzuki reactions of a wide variety of arylboronic acids and aryl chlorides, bromides, and iodides to afford the desired biaryl products in high isolated yields. Arylboronic acids and aryl chlorides containing electron-poor, electron-rich, and ortho substituents participate effectively. In contrast, the structurally related ligand 2-(2'-dicyclohexylphosphinophenyl)-1,3-dioxolane (ligand 2) was found to be less efficient under similar conditions. The reaction of ligand 1 with Pd(dba)(2) affords the complex LPd(dba) (14, L = 1). The NMR spectroscopic and X-ray crystallographic data of complex 14 establish that ligand 1 functions as a P,O-chelating ligand in complex 14. The reaction of ligand 2 (2 equiv) with Pd(dba)(2) and excess 4-(t)()Bu-C(6)H(4)Br or the ligand displacement reaction of {Pd[P(o-tolyl)(3)](4-(t)()Bu-C(6)H(4))(&mgr;-Br)}(2) with ligand 2 affords the bis-phosphine complex L(2)Pd(4-(t)()Bu-C(6)H(4))(Br) (13, L = 2). The NMR spectroscopic data of complex 13 establish that ligand 2 in complex 13 functions as a nonchelating ligand. Thus, the higher efficiency of ligand 1 over ligand 2 in Pd/L-catalyzed Suzuki arylation of aryl chlorides can be ascribed to the ability of ligand 1 to generate and stabilize mono-phosphine P,O-chelating Pd/L intermediates, which appear to be most suitable for Suzuki arylation reactions involving certain substrates and conditions.