A series of copper, cobalt, nickel and manganese complexes were synthesized and characterized. Reaction of 5-amino-2-cyanopyridine with MCl2⋅xH2O (M: Cu2+, Co2+, Ni2+, Mn2+) in anhydrous ethanol resulted in the formation of four complexes [NH2EtPyCuCl2(CH3OH)].H2O 1, [(NH2EtPyHCl)3Co] (Cl)3.3H2O 2, [(NH2EtPy)22(H2O)Ni](Cl2) 3, and [(NH2EtPy)22(H2O)Mn](Cl2) 4 [NH2EtPy=5-amino-o-ethylpyridine-2-carboximidate], respectively. The structures of these compounds were determined by X-ray diffraction, NMR and IR spectroscopy, and elemental analysis. Each complex was then used as a catalyst in the Henry reaction, and its catalytic activity was determined by 1H NMR. Good catalytic effects were achieved (69–87%).

The compound I (C7H7NO2, salicylamide) and the compound II (C16H12N2, 2,5-diphenylpyrazine) were both obtained as the by-product of the one-pot synthesis of oxazolinyl zinc complexes from the reaction of 2-hydroxybenzonitrile and 3-(N-ethyl-N-phenyl)-propanenitrile with d-phenylalaninol, which was catalyzed by 235 and 83.1 mol% zinc dichloride. Their structures were determined by X-ray diffraction, IR ,and elemental analysis.

A series of 2-oxazolines were synthesized using a simple, one-pot method under inert, moisture-free conditions from the benzoylacetonitrile and β-aminoalcohols mediated by 115–172 mol% ZnCl2. Structures of products were fully characterized by NMR, IR and MS.

Two novel chiral amino alcohol-nickel complexes (I) and (II) have been first reported from the direct reaction of L-plenylglycinol with Ni(OAc)2 · 4H2O in anhydrous ethanol and L-phenylalaninol with NiCl2 · 6H2O in anhydrous methanol. The crystal structures of I and II were determined by X-ray diffraction and further characterized by elemental analysis and IR. For I: C24H31N3NiO3, monoclinic, P21, a = 5.2581(12), b = 23.683(5), c = 13.744(3) Å, β = 97.939(6)°, V = 1695.1(7) Å3, Z = 2, ρcalcd = 0.917 g/cm3, the final R factor was R1 = 0.0897, 5315 for reflections were observed with I0 > 2σ(I0); for II: C27H43Cl2N3NiO5, orthorhombic, P212121, a = 9.844(3), b = 12.373(3), c = 26.158(7) Å, V = 3186.3(14) Å3, Z = 4, ρcalcd = 1.291 g/cm3, the final R factor was R1 = 0.0371, 6265 for reflections were observed with I > 2σ(I).

Treatment in different proportions of 1,2-diaminobenzene with Ni(OAc)2 · 4H2O in methanol results in the formation of two 1,2-diaminobenzene-Ni complexes I (C92H134N24Ni9O28) and II (C16H22N4NiO4). Their structures were determined by X-ray diffraction analysis. The complexes are also characterized by elemental analysis and IR.

Two opposite configuration (R/S) of chiral complexes (C8H11N)2 · Zn(OAc)2 (Ia and Ib—L-(−)-) and D-(+)-isomer) were synthesized by a simple one-pot method. The crystal structures of Ia and ib determined by X-ray crystallography.

Compound I, [di-μ-methoxo-bis[(2-aminopyridine)(chloro)copper(II)], was obtained by two different synthetic routes. In synthetic route 1, we first obtained intermediate by the addition of two equivalents of o-aminopyridine to copper chloride in an ethanolic solution, and then we recrystallized the intermediate from methanol and n-hexane to give compound I. Synthetic route 2 involved the reaction of o-aminopyridine with copper chloride in a methanol solution directly. The crystal structure of compound I was obtained. The reaction of m-xylylenediamine with Zn(OAc)2 · 2H2O in THF resulted in the production of one novel zinc complex C12H18N2O4Zn, bis(m-xylenediamine)zinc (II) and its structure was determined by X-ray diffraction analysis. Complexes I and II were also characterized by elemental analysis, and IR. Then they were applied as catalysts for the Henry reaction, and they achieved good conversions (64 and > 99%, respectively).

(C8H11N)2·Zn(OAc)2 (1a), (C8H11N)2·Cu(OAc)2 (1b), and (C8H11N)2·CuCl2 complexes are synthesized by a simple one-pot method. The crystal structures of 1a, 1b, and 1c are determined by X-ray crystallography. The complexes are also characterized by NMR, IR, MS, and elemental analysis and used as the catalysts applied to the Henry reaction; moderate to high yields are obtained at room temperature.

Dimethyldimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane have been synthesized by a one-step, simple method and used as catalysts in the Henry reaction with Cu(OAc)2·H2O and Zn(OAc)2·2H2O, affording 60–96% conversion under the optimum catalytic conditions.

Chiral α-ethylphenylamine tartaric acid salts were synthesized from α-ethylphenylamine by direct reaction with chiral tartaric acid. The crystal structure of S-(−)-α-ethylphenylamine-(2R,3R)-(−)-dihydroxybutanedioic acid was determined. The crystal is monoclinic, of space group P21/n, with a = 6.331(5) Å, b = 14.209(11) Å, c = 7.495(6) Å, α = 90.00º, β = 107.000(13)º, γ = 90.00º, λ = 0.7103 Ǻ, V = 644.7(9), Z = 2, Dc = 1.397 g/cm3, Mr = 271.27 and F(000) = 288, R = 0.0477, and ωR = 0.0838 for 1388 observed reflections with I > 2σ(I). We then used the chiral α-ethylphenylamine tartaric acid salts as catalysts in the cyanosilylation of prochiral ketones, and moderate conversions were obtained.

A class of modular oxazolines and their derivatives 1−5 were synthesized with moderate to excellent yields using a simple one-pot method; 4 × 3 bis-oxazolines were obtained, as expected, from each of the three reactions of 1,4-dicyanobenzene, 1,3-dicyanobenzene, and 1,2-dicyanobenzene with optically active amino alcohols in chlorobenzene under dry, anaerobic conditions. ZnCl2 was used as a Lewis acid catalyst. Direct condensation of 1, 2-bis(cyanomethyl) benzene or 2-cyanophenylacetonitrile did not yield the target products, but two series of novel compounds (4 and 5) were isolated and their structures were confirmed by X-Ray analysis. All products (1−5) were characterized by NMR, IR, and MS.

A novel family of oxazolinyl copper(II) catalysts have been developed and used as Lewis acid catalysts in the asymmetric Henry reaction of various aldehydes with nitromethane. The corresponding nitroalcohol products were obtained in moderate yields (40–80%) and with moderate enantioselectivity (10–40% ee).

The treatment of o-diaminobenzene with Zn ( OAc )2 · 2H2O in alcohol results in the formation of mononuclear bis(o-diaminobenzene)diacetate Zinc, Zn[C8H11N2O2]2. Its structure was determined by X-ray diffraction analysis. The complex is also characterized by elemental analysis, 1H NMR and IR. The crystal is monoclinic space group C2, parameters: a = 16.297(5), b = 4.775(3), c = 11.664(5) Å, β = 97.646(5)°, λ = 1.54184 Å, V = 899.6(7) Å3, Z = 2, ρc = 1.476 g/cm3, Mr = 399.75, F(000) = 416.0, R1 = 0.0594, wR2 = 0.1439 for 995 observed reflections with I > 2σ(I).

The synthesis and characterization of a series of N-Zn, N-Cu complexes with 2-amino pyridine and ethylenediamine ligands (1a–b and 2a–b) have been described. They were synthesized with a simple, one-pot method, and the crystal structures of 1a, 1b, 2a and 2b were determined by X-ray crystallography. The complexes were also characterized by NMR, IR, and elemental analysis. They were used as the catalysts in an application to the Henry reaction, and high yields were obtained under the optimum conditions.