Stereoselective Fluorosulfonylation of Vinylboronic Acids for (E)-Vinyl Sulfonyl Fluorides with Copper Participation.

A practical synthetic method for the synthesis of vinyl sulfonyl fluorides through copper-promoted direct fluorosulfonylation has been developed. The reaction of the vinylboronic acids with DABSO and then NFSI is performed under mild reaction conditions. This transformation efficiently affords aryl or alkyl vinyl sulfonyl fluorides with good reaction yields, exclusive E-configuration, broad substrate scope, excellent compatibility, and operational simplicity.

Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3.

Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.

Geometrically Selective Denitrative Trifluoromethylthiolation of ß-Nitrostyrenes with AgSCF3 for (E)-Vinyl Trifluoromethyl Thioethers.

An efficient copper(II)-promoted denitrative trifluoromethylthiolation under mild reaction conditions has been developed for vinyl trifluoromethyl thioethers to construct Cvinyl-SCF3 bonds with stable AgSCF3 as a source of the trifluoromethylthio. This reaction system tolerates a broad range of functional groups to commendably achieve a high product yield and excellent stereoselectivity of E/Z.

Zinc-Mediated Intermolecular Reductive Radical Fluoroalkylsulfination of Unsaturated Carbon-Carbon Bonds with Fluoroalkyl Bromides and Sulfur Dioxide.

A versatile and general zinc-mediated intermolecular reductive radical fluoroalkylsulfination of unsaturated C-C bonds has been developed using readily available fluoroalkyl bromides and 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct (DABSO) with wide substrate scope and excellent functional group tolerance. Sulfur dioxide anion radical generated in situ from the reduction of sulfur dioxide with zinc may be involved in the reaction mechanism.

Crystal structure of poly[[µ-1,1'-(butane-1,4-di-yl)bis-(1H-benzimidazole)-κ(2) N (3):N (3')]{µ-4,4'-[1,4-phenyl-enebis(-oxy)]di-ben-zo-ato-κ(4) O,O':O'',O'''}cobalt(II)].

In the title compound, [Co(C20H12O6)(C18H18N4)] n , the Co(II) atom, located on a twofold rotation axis, is hexa-coordinated to four O from two bis-bidentate 4,4'-[phenyl-enebis(-oxy)]dibenzoate (L) ligands and two N atoms from two 1,1'-(butane-1,4-di-yl)bis-(1H-benzimidazole) (bbbm) ligands, forming a distorted octahedral cis-N2O4 coordination environment. Polymeric zigzag chains along [102] are built up by the bridging L ligands. These chains are additionally connected by the bbbm ligands to produce a two-dimensional coordination polymer parallel too (010).

Crystal structure of (4-fluoro-phenyl-κC (1))iodido-(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ(2) N,N')palladium(II).

In the title compound, [Pd(C6H4F)I(C6H16N2)], the Pd(II) atom is coordinated by two N atoms from the N,N,N',N'-tetra-methyl-ethylenedi-amine ligand, a C atom of the 4-fluoro-phenyl group and an iodide ligand in a distorted square-planar geometry, with an average deviation from the least-squares plane through the ligand donor atoms of 0.0159 (2) Å. The angles about the Pd(II) atom range from 83.35 (16) to 178.59 (11)°. In the crystal, weak C-H⋯F and C-H⋯I hydrogen bonds link the mol-ecules into sheets in the bc plane.

(4-Fluoro-phen-yl-κC)(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ(2) N,N')(tri-fluoro-meth-yl-κC)palladium(II).

In the title compound, [Pd(CF3)(C6H4F)(C6H16N2)], the Pd(II) cation is four-coordinated by the two N atoms of the N,N,N',N'-tetra-methyl-ethylenedi-amine ligand and by one C atom each from a 4-fluoro-phenyl and a tri-fluoro-methyl ligand, in a distorted rectangular-planar geometry, with an average deviation from the least-squares plane of 0.066 (2) Å. The central coordination angles with the Pd(II) atom range from 83.14 (10) to 97.25 (12)°.

catena-Poly[[di-aqua-[µ2-4-(4-carb-oxy-phen-oxy)benzoato](µ2-4,4'-oxydibenzo-ato)praseodymium(III)] monohydrate].

In the title compound, {[Pr(C14H8O5)(C14H9O5)(H2O)2]·H2O} n , the Pr(III) cation is eight-coordinated by six carboxyl O atoms from both a monoanionic 4-(4-carb-oxy-phen-oxy)benzoate and a dianionic 4,4'-oxydibenzoate ligand (four bridging with two from a bidentate chelate inter-action), and two O-atom donors from water mol-ecules. A single water mol-ecule of solvation is also present. The complex units are linked through carboxyl O:O' bridges giving a two-dimensional sheet polymer lying parallel to (001). An overall three-dimensional network structure is generated through inter-molecular carb-oxy-lic acid and water O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions.

2,3-Bis(furan-2-yl)pyrazino-[2,3-f][1,10]phenanthroline.

The mol-ecule of the title compound, C22H12N4O2, is located on a twofold rotation axis. The dihedral angle between the furan and pyrazine rings is 34.8 (7)°, and that between the furan rings is 46.92 (7)°. A π-π stacking interaction occurs between adjacent pyrazino[2,3-f][1,10]phenanthroline units, with an interplanar distance of 3.5862 (12) Å.

Catalytic conversion of cellulose to 5-hydroxymethyl furfural using acidic ionic liquids and co-catalyst.

Efficient catalytic conversion of microcrystalline cellulose (MCC) to 5-hydroxymethyl furfural (HMF), is achieved using acidic ionic liquids (ILs) as the catalysts and metal salts as co-catalysts in the solvent of 1-ethyl-3-methylimidazo-lium acetate ([emim][Ac]). A series of acidic ILs has been synthesized and tested in conversion of MCC to HMF. The effect of reaction conditions, such as reaction time, temperature, catalyst dosage, metal salts, water dosage, Cu(2+) concentration and various acidic ILs are investigated in detail. The results show that CuCl(2) in 1-(4-sulfonic acid) butyl-3-methylimidazolium methyl sulfate ([C(4)SO(3)Hmim][CH(3)SO(3)]), is found to be an efficient catalyst for catalytic conversion of MCC to HMF, and 69.7% yield of HMF is obtained. A mechanism to explain the high activity of CuCl(2) in [C(4)SO(3)Hmim][CH(3)SO(3)] is proposed. To the best of our knowledge, this report first proposes that the Cu(2+) and [C(4)SO(3)Hmim][CH(3)SO(3)] show better catalytic performance in catalytic conversion of MCC to HMF.

catena-Poly[[diaqua-bis(1H-imidazole-κN(3))cobalt(II)]-µ-2,3,5,6-tetra-chloro-tereph-thal-ato-κ(2)O(1):O(4)].

In the title compound, [Co(C(8)Cl(4)O(4))(C(3)H(4)N(2))(2)(H(2)O)(2)](n), the Co(II) ion displays a distorted octa-hedral coordination geometry with two O atoms from two monodentate tetra-chloro-terephthalate dianions, two N atoms from two imidazole mol-ecules and two O atoms from two water mol-ecules. The Co(II) ions are connected via the tetra-chloro-terephthalate dianions into a chain running along the crystallographic [110] direction. Adjacent chains are linked into a two-dimensional network arranged parallel to (010) by classical N-H⋯O and O-H⋯O hydrogen bonds.

2,3-Bis(thio-phen-2-yl)pyrazine-[2,3-f][1,10]phenanthroline.

The mol-ecule of the title compound, C(22)H(12)N(4)S(2), shows no crystallographic symmetry. The thiophene rings form different dihedral angles [40.15 (9) and 15.43 (10)°] with the pyrazine ring. A strong π-π stacking inter-action occurs between adjacent pyrazine-[2,3-f][1,10]phenanthroline units with an inter-planar distance of 3.4352 (16) Å.

4,4'-Bis(trimethyl-sil-yl)-2,2'-bipyridine.

In the mol-ecule of title compound, C(16)H(24)N(2)Si(2), the pyridine rings are nearly planar (r.m.s. deviation = 0.002 Å).

catena-Poly[[[aqua-tris-(pyridine-κN)nickel(II)]-µ-2,3,5,6-tetra-chloro-benzene-1,4-dicarboxyl-ato-κO:O] pyridine monosolvate].

The asymmetric unit of the title compound, {[Ni(C(8)Cl(4)O(4))(C(5)H(5)N)(3)(H(2)O)]·C(5)H(5)N}(n), contains two independent nickel(II) cations displaying a distorted octa-hedral coordination geometry provided by the N atoms of three pyridine mol-ecules, the O atom of a water mol-ecule, and O atoms of two monodentate µ(2)-bridging tetra-chloro-terephthalate dianions. The metal atoms are linked by the dianions into zigzag chains running parallel to [11]. The crystal packing is stabilized by O-H⋯N and O-H⋯O hydrogen bonds.

Novozyme 435-catalyzed efficient acylation of 3-n-butylphthalide in organic medium.

Novozyme 435 could catalyze efficient acylation of 3-n-butylphthalide in organic medium. The conversion of 3-n-butylphthalide increased with the increase of hydrophobicity of solvent below that of hexane. The more available solvent was hexane. Salt hydride could control fixed water activity. The optimum water activity was 0.62. And the optimum of reaction time, velocity of agitation, dosage of Novozyme 435 and acetic anhydride to 3-n-butylphtrhalide molar ratio were 48 hours, 150 rpm, 8 mg/mL and 8:1, respectively. The conversion of 48.9% could be obtained at a water activity of 0.62 in hexane. Furthermore, Novozyme 435 had an enantioselective acylation of racemic 3-n-butylphthalide by original analysis.

catena-Poly[[bis-(methanol-κO)bis-(pyridine-κN)nickel(II)]-µ-tetra-fluoro-terephthalato-κO:O'].

In the title compound, [Ni(C(8)F(4)O(4))(C(5)H(5)N)(2)(CH(4)O)(2)](n), the Ni(II) ion is located on an inversion center and is coordinated by four O atoms [Ni-O = 2.079 (4) Å] from two tetra-fluoro-terephthalate ligands and two methanol mol-ecules, and by two N atoms [Ni-N = 2.127 (4) Å] from two pyridine ligands in a distorted octa-hedral geometry. The Ni(II) ions are connected via the tetra-fluoro-terephthalate anions into a one-dimensional chain running along the crystallographic [011] direction.

catena-Poly[[tris-(pyridine-κN)copper(II)]-µ-tetra-fluoro-terephthalato-κO:O].

In the title compound, [Cu(C(8)F(4)O(4))(C(5)H(5)N)(3)](n), the Cu(II) atom, lying on a twofold rotation axis, is five-coordinated by two O atoms from two tetra-fluoro-terephthalate ligands and three N atoms from three pyridine ligands in a distorted trigonal-bipyramidal geometry. Adjacent Cu(II) atoms are connected via the bridging tetra-fluoro-terephthalate ligands into a one-dimensional chain running along the [101] direction.