New Chiral Diamines of the Dioxolane Series: (+)-(4S,5S)-2,2-Dimethyl-4,5-bis(diphenylaminomethyl)- 1,3-dioxolane and (+)-(4S,5S)-2,2-Dimethyl-4,5-bis(methyl- aminomethyl)-1,3-dioxolane

The reaction of sodium diphenylamide with 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane gave (+)-(4S,5S)-2,2-dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane, which was brought into complex formation with cobalt chloride. Treatment of 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane with sodium N-methylanilide resulted in cleavage of the SÄO bond in the p-toluenesulfonate moiety with formation of N-methyl-N-phenyl-p-toluenesulfonamide and 4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane disodium salt. Diethyl (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate reacted with methylamine to give the corresponding dicarboxamide which was reduced with lithium aluminum hydride to (4S,5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane having chiral carbon and nitrogen atoms.     

Coordinating properties of C2-symmetric chiral bis(oxazolinylpyridinyl)dioxolane ligands

Metal complexes of general formula M(L)X₂ and M(L)X₃ [L = (4S,5S)-2,2-dimethyl-4,5-bis{6-[(4,5-dihydro-4-(S)-(1-methylethyl)oxazol-2-yl)pyridin-2-yl]}-1,3-dioxolane] were obtained by reacting, respectively, Co^II, Cu^II, Ni^II, and Zn^II nitrate salts and the Rh^III chloride salt, with a chiral C₂-symmetric bis(oxazolinylpyridinyl)dioxolane (L) ligand, in MeOH/CHCl₃ solution. A single crystal X-ray analysis was carried out on [Ni(L)(OH₂)₂](NO₃)₂ · 2H₂O and the molecular structure of L was also determined. In the free ligand the two symmetric arms are essentially planar and oriented nearly perpendicular to the dioxolane average plane. In the Ni complex one seven-membered and two five-membered chelation rings are formed. The metal atom also lies on the C₂ axis, and two symmetry-related water molecules complete the octahedral coordination environment. Both compounds crystallize in chiral space groups; the ligand crystallizes in orthorhombic system, space group C 2 2 2₁, Z = 4; the nickel complex crystallizes in tetragonal system, space group P 4₃ 2₁ 2, Z = 4.     

Enantioselective Hydrogenation over Chiral Cobalt Complexes with (+)-(1S,2S,5R)-Neomenthyldiphenylphosphine and (-)-(R,R)-2,2-Dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane

The optical yield in enantioselective hydrogenation of methyl -acetamidocinnamate over mono- and diphosphine cobalt(II) complexes CoX₂L₂ [where X = Cl or CF₃SO₃, L = (+)-(1S,2S,5R)-neomenthyl-diphenylphosphine or L2' = (-)-(R,R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane], which are generated in situ, in the presence of sodium tetrahydridoborate increases with rise in the phosphine-to-metal ratio and hydrogen pressure. The maximal optical yields of (+)-(S)-N-acetylphenylalanine methyl ester attain 40% (CoX₂L₂) and 42% (CoX₂L₂').     

Convenient synthesis of （4R,5R）-4,5-bis（aminomethyl）-2-isopropyl- 1,3-dioxolane

A convenient approach for the preparation of (4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane is described. The target compound via two steps is synthesized from diethyl-2,3-O-isobutylidene-D-tartrate, through ammonolysis and reduction.     

Rhodium dimers with 2,2-dimethyl-1,3-diisocyano and bis(diphenylphosphino)methane bridging ligands

Four rhodium dimers have been synthesized with a bridging diisocyanide ligand, dmb (2,2-dimethyl-1,3-diisocyanopropane): [Rh2(dmb)4](BPh4)2, [Rh2(dmb)4Cl2]Cl2, [Rh2(dmb)4I2](PF6)2, and [Rh2(dmb)2(dppm)2](BPh4)2 (dppm = bis(diphenylphosphino)methane). The complexes have been characterized by elemental analysis and mass spectrometry, as well as UV-visible, IR, and 1H NMR spectroscopies. X-ray crystal structures of the rhodium(I) complexes, [Rh2(dmb)4](BPh4)2 . 1.5CH3CN (3.2330(4), 3.2265(4) A) and [Rh2(dmb)2(dppm)2](BPh4)2.0.5CH3OH . 0.2H2O (3.0371(5) A), confirm the existence of short Rh...Rh interactions. The metal-metal separation for the rhodium(II) adduct, [Rh(2)(dmb)4Cl2]Cl2.6CHCl3 (2.8465(6) A), is consistent with a formal Rh-Rh bond. For the two luminescent rhodium(I) dimers and six previously investigated diisocyano-bridged dimers with and without dppm ligands, the intense spin-allowed dsigma-->psigma absorption band maximum shifts to longer wavelengths with decreasing Rh...Rh separation, and there is an approximate correlation between band energy and the inverse of the metal-metal separation cubed. Both [Rh2(dmb)4]2+ and [Rh2(dmb)4(dppm)2]2+ undergo oxidative addition in the presence of iodine. In the conversion of [Rh2(dmb)4]2+ to [Rh2(dmb)4I2]2+, the observed intermediate is tentatively assigned to a tetramer composed of two rhodium dimers. In the case of [Rh2(dmb)2(dppm)2]2+, no intermediate was detected.     

Synthesis and metal complexes of chiral c(2)-symmetric diamino-bisoxazoline ligands

A synthetic route to tetradentate chiral N(4) ligands has been developed with the aim to study the potential of corresponding iron and manganese complexes as catalysts for enantioselective epoxidation. These ligands, which contain two oxazoline rings and two trialkylamino groups as coordinating units, are readily prepared in enantiomerically pure form by the reaction of chiral 2-chloromethyloxazolines with achiral N,N'-dimethylethane-1,2-diamine or chiral (R,R)-N,N'-dimethylcyclohexane-1,2-diamine. The ligands derived from N,N'-dimethylethane-1,2-diamine reacted with anhydrous metal halides MnCl(2) and FeCl(2) in a stereoselective manner to give octahedral mononuclear complexes that have the general formula Delta-[(L)MCl(2)]. In contrast, the ligands derived from N,N'-dimethylcyclohexane-1,2-diamine formed complexes with different coordination modes depending on the diastereomer employed: in one case the metal ion was found to be pentacoordinate, in the other case a hexacoordinated complex was observed. The structure of a series of Fe and Mn complexes was determined by X-ray analysis. The coordination chemistry of these ligands was further studied by X-ray and NMR analyses of the diamagnetic isostructural complexes [(L)ZnCl(2)]. Analogous ionic complexes, which were prepared by removing chloride with silver trifluoromethanesulfonate or hexafluoroantimonate, were tested as catalysts for the epoxidation of olefins.     

2-芳基-(4S,5S)-4,5-双(胺甲酰基)-1,3-二氧戊环的合成

以D-酒石酸二乙酯和芳香醛为原料,经缩醛化、氨解两步反应合成了15个未见文献报道的适合工业化生产庚铂类似物的关键中间体——2-芳基-(4S,5S)-4,5-双(胺甲酰基)-1,3-二氧戊环,产率49%～70%,其结构经1HNMR和MS表征。     

Main group complexes incorporating 1,3-bis(furyl)-1,1,3,3-tetramethyldisilazide ligands

The lithium salt of the bis-furyl substituted disilazide anion, Li{i} [{i} = N(SiMe₂R)₂ where R = 2-methylfuryl] has been examined as a ligand transfer reagent for the synthesis of group 2 (magnesium) and group 13 (aluminium) compounds. Salt metathesis between Li{i} and AlMe₂Cl afforded the expected dimethyl species, Al{i}Me₂ (1), which was isolated as a colourless oil. In contrast the corresponding aluminium dichloride, synthesized from Li{i} and AlCl₃, gave crystalline products as both the THF adduct Al{i}Cl₂(THF) (2a) and the base-free derivative, Al{i}Cl₂ (2b). The homoleptic magnesium bis(amide) Mg{i}₂ (3) was also synthesized. X-ray crystallographic analysis of 2a reveals a four-coordinate distorted tetrahedral metal, in which neither of the furyl-substituents interact with the metal. In contrast, the aluminium in the base-free dichloride 2b is five-coordinate, containing the first structurally characterized example in which the amide binds with a κ¹N,O,O′-bonding mode, involving coordination of both furyl-substituents at the N-bound metal.     

Synthesis, crystal structure and characterization of photochromic 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene

A novel photochromic diarylethene, 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene (BEDTP), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its photochromic and fluorescent properties were also investigated. The results showed that this compound exhibited reversible photochromism, changing from colorless to magenta after irradiation with UV light both in solution and in the crystalline phase. In hexane solution, the open-ring isomer of BEDTP exhibited relatively strong fluorescence at 400 nm when excited at 282 nm. The fluorescence intensity decreased along with the photochromism upon irradiation with 254 nm light and its closed-ring isomer showed almost no fluorescence.