Aerobic oxidation of alcohols and the synthesis of benzoxazoles catalyzed by a cuprocupric coordination polymer (Cu(+)-CP) assisted by TEMPO.

A Cu(+)-CP based on the tetranuclear unit {[(HSQPA)2Cu4(bipy)4]·2H2O}n·2nH2O has been constructed through Cu(2+) salt, 2-(sulfonylquinlium-8-yloxy)phthalic acid (H3SQPA), and 4,4'-bipyridine (bipy). This Cu(+)-CP combined with 2,2,6,6-tetramethylpiperidine-1-oxyl as the cocatalyst is an effective catalyst for aerobic oxidation of alcohols and the synthesis of benzoxazoles and can be recycled at least four times without losing its catalytic activity.

N-Heterocyclic carbene (NHC)-modulated Pd/Cu cocatalyzed three-component synthesis of 2,6-diarylquinolines.

Two new NHC adducts of cyclopalladated ferrocenylpyrazine complexes 1-2 have been prepared and characterized. An efficient NHC-modulated Pd/Cu cocatalyzed three-component coupling reaction for the synthesis of 2,6-diarylquinolines from aminobenzyl alcohols, aryl ketones, and arylboronic acids in air is described. The reaction involves oxidation, cyclization and Suzuki reactions. The luminescence of the resulting arylquinolines 3-30 was also investigated.

One-pot synthesis of ferrocenyl ketones containing biaryls and 6-aryl-2-ferrocenylquinolines via Ir/Pd-cocatalyzed α-alkylation/Suzuki reaction.

An efficient PPh3-cyclometalated iridium(III) benzo[h]quinoline hydride 1/Pd(OAc)2-cocatalyzed three-component α-alkylation/Suzuki reaction has been developed. The three-component reaction of 4-bromobenzyl alcohol, acetylferrocene, and arylboronic acids gives ferrocenyl ketones containing biaryls in moderate to good yields. This method was successfully applied to a one-pot synthesis of 6-aryl-2-ferrocenyl quinolines, using (2-amino-5-bromophenyl)methanol instead of 4-bromobenzyl alcohol.

2,2'-Dimeth-oxy-6,6'-dinitro-biphen-yl.

In the title compound, C(14)H(12)N(2)O(6), the half mol-ecule in the asymmetric unit of the cell is completed by a crystallographic twofold rotation axis, and the two benzene rings of the complete mol-ecule make a dihedral angle of 60.5 (3)°. Furthermore, inter-molecular weak C-H⋯O hydrogen bonds link adjacent mol-ecules, forming a two-dimensional sheet. These sheets are stablized by face-to-face weak π-π contacts [centroid-centroid distance = 3.682 (1) Å] between the nearly parallel [dihedral angle = 0.12 (7)°] benzene rings of the neighboring mol-ecules, resulting in a three-dimensional network.

4,6-Dimethyl-2-p-tolyl-pyrimidine.

The mol-ecule of the title compound, C(13)H(14)N(2), is located on a crystallographic mirror plane. The aromatic rings make a dihedral angle of 3.4 (2)°. The H atoms of the methyl groups on the benzene ring are disordered over two positions; their site-occupation factors were fixed at 0.5. In the crystal, inter-molecular C-H⋯π contacts form infinite chains perpendicular to the b axis.

1-Bromo-3,5-diphenyl-benzene.

The title compound, C(18)H(13)Br, crystallizes with two crystallographically independent mol-ecules in the asymmetric unit. The C-Br bond lengths and the C-C bond lengths between the benzene rings are slightly different in the two mol-ecules. The dihedral angles between adjacent benzene rings are 26.85 (2) and 39.99 (2)° in one mol-ecule, and 29.90 (2) and 38.01 (2)° in the other. There are three types of inter-molecular C-H⋯π inter-actions in the crystal structure.

Bis(3-meth-oxy-6-methyl-2-pyrid-yl) ether.

In the mol-ecule of the title compound, C(14)H(16)N(2)O(3), the dihedral angle between the pyridyl rings is 87.74 (3)°. In the crystal structure, inter-molecular C-H⋯O hydrogen bonds link the mol-ecules into infinite zigzag chains.

6,6'-Dimeth-oxy-2,2',3,3',5-penta-nitro-1,1'-biphen-yl.

In the axially chiral title compound, C(14)H(9)N(5)O(12), the dihedral angle between the two benzene rings is 86.0 (8)°. In the crystal structure, the mol-ecules display a two-dimensional framework formed by weak inter-molecular C-H⋯O hydrogen bonds.

2,4,6-Trimethyl-1,3,5-tris-(morpholino-meth-yl)benzene.

In the title compound, C(24)H(39)N(3)O(3), the H atoms of the methyl groups are disordered over two positions, with site-occupation factors fixed at 0.5. The three morpholino groups are arranged in an asymmetrical fashion with respect to the anchoring mesitylene ring and adopt chair conformations. Inter-molecular C-H⋯π inter-actions link the mol-ecules into a one-dimensional chain structure.

N,N-Bis(2-hydroxy-benzyl-idene)-2,2'-bipyridyl-3,3'-dicarbohydrazide.

In the title compound, C(26)H(20)N(6)O(4), the two aroylhydrazone side groups exist as diastereomeres, both in the keto form in the crystal structure. The aroylhydrazone units support the mol-ecular conformation through an intra-molecular N-H⋯O hydrogen bond. Two mol-ecules are connected into a centrosymmetric dimer by inter-molecular N-H⋯N hydrogen bonds. These dimers are connected into chains along the a axis by inter-molecular O-H⋯O hydrogen bonds. The combination of these hydrogen bonds results in layers in the bc plane. The layers are further linked by weak C-H⋯π contacts to form a three-dimensional network structure.

1,3,5-Tris{[3-(1H-benzotriazol-1-ylmeth-yl)phen-oxy]meth-yl}-2,4,6-trimethyl-benzene.

In the title compound, C(51)H(45)N(9)O(3), three 1-(1H-benzotriazol-1-ylmeth-yl)-3-phen-yloxy (bmph) ligands are bonded to the central benzene ring in an asymmetric arrangement, two bmph located on one side of the central benzene ring and the other bmph located on the opposite side of the central benzene ring. The dihedral angles between the central benzene ring and the three pendant phenoxy rings are 76.71 (14), 67.81 (13) and 70.67 (16)°. In the crystal structure, one bmph is disordered over two sites in a 0.611 (5):0.389 (5) ratio. Some of the methyl H atoms are equally disordered over two sets of sites. Inter-molecular C-H⋯N hydrogen bonding is present in the crystal structure.

2-Ferrocenyl-6-methyl-pyridin-3-ol.

In the title compound, [Fe(C(5)H(5))(C(11)H(10)NO)], the dihedral angle between the pyridyl and substituted cyclo-penta-dienyl rings is 20.4 (3)°. The H atoms of the methyl group are disordered over two positions; their site-occupation factors were fixed at 0.5. The crystal structure is stabilized by well defined inter-molecular O-H⋯N and C-H⋯O hydrogen bonds, leading to the formation of a two-dimensional network parallel to (101).

Cyclometalated Pd(II) and Ir(III) 2-(4-bromophenyl)pyridine complexes with N-heterocyclic carbenes (NHCs) and acetylacetonate (acac): synthesis, structures, luminescent properties and application in one-pot oxidation/Suzuki coupling of aryl chlorides containing hydroxymethyl.

A series of cyclopalladated 2-(4-bromophenyl)pyridine (bpp) complexes [Pd(bpp)(NHC)Cl] 1-3, [Pd(bpp)(acac)] 4, cyclometalated iridium(iii) complexes [Ir(bpp)2Cl]25 and [Ir(bpp)2(acac)] 6 have been synthesized and characterized. Their detailed structures have been determined by X-ray diffraction and many intermolecular C-HX (Cl, Br, π) and ππ interactions were found in their crystals. Cyclometalated complexes 1-4 and 6 exhibit luminescence with emission peaks of 390-543 nm in dichloromethane solution under UV irradiation. Their application to coupling reactions of aryl chlorides containing hydroxymethyl was also investigated. An efficient 3/Cu cocatalyzed oxidation/Suzuki reaction for the synthesis of biarylaldehydes from chloro-phenylmethanol and arylboronic acids in air has been developed. In addition, a 6/3-cocatalyzed one-pot reaction of acetylferrocene, (2-amino-5-chlorophenyl)methanol, and arylboronic acids provided 6-aryl-2-ferrocenylquinolines in moderate to good yields.

A new copper-based metal-organic framework as a promising heterogeneous catalyst for chemo- and regio-selective enamination of ß-ketoesters.

Assembly of 5-nitro-1,2,3-benzenetricarboxylic acid (H3nbta) with Cu(II) in the presence of 1,3-bis(1,2,4-triazol-1-yl)propane (1,3-btp) leads to a new metal-organic framework, [Cu(Hnbta)(1,3-btp)]·2H2O (A1), which is shown to be an efficient and recyclable heterogeneous catalyst for enamination of ß-ketoesters with excellent product yields and selectivity.

Design and synthesis of tetranuclear cluster monophosphine-cyclopalladated ferrocenylpyrimidinone complexes from the palladium-catalyzed hydroxylation of chloropyrimidine.

Hydroxylation of a monomeric triphenylphosphine-cyclopalladated ferrocenylchloropyrimidine [PdCl{[(eta(5)-C(5)H(5))]Fe[(eta(5)-C(5)H(3))-N(2)C(4)H(2)-Cl]}(PPh(3))] with KOH gave the first example of a tetranuclear cluster monophosphine-palladacycle [Pd{[(eta(5)-C(5)H(5))]Fe[(eta(5)-C(5)H(3))-N(2)C(4)H(2)O]}(PPh(3))](4). Additionally, the analogous tricyclohexylphosphine tetranuclear cluster palladacycle has also been successfully synthesized by the same method.