Synthesis of 1-deoxy-D-galactohomonojirimycin via enantiomerically pure allenylstannanes

1-Deoxy-D-galactohomonojirimycin was synthesized in seven steps from optically pure allenylstannane 4 and L-lactate-derived aldehyde 5 in 48% overall yield. The key step was the Lewis acid catalyzed reaction of 4 and 5 to give the syn-amino alcohol in excellent yield and very high diastereoselectivity.     

Comparison of uranyl extraction mechanisms in an ionic liquid by use of malonamide or malonamide-functionalized ionic liquid

The extraction of uranyl from acidic (HNO(3)) aqueous solutions toward an ionic liquid phase, C(1)-C(4)-imTf(2)N (1-methyl,3-butylimidazolium Tf(2)N), has been investigated as a function of initial acid concentration and ligand concentration for two different extracting moieties: a classical malonamide, N,N'-dimethyl-N,N'-dibutylmalonamide (DMDBMA) and a functionalized IL composed of the Tf(2)N(-) anion and an imidazolium cation on which a malonamide pattern has been grafted (FIL-MA). The extraction mechanism, as demonstrated through the influence of added C(1)-C(4)-imCl or added LiTf(2)N in the aqueous phase, is slightly different between the DMDBMA and FIL-MA extracting agents. Modeling of the extraction data evidences a double extraction mechanism, with cation exchange of UO(2)(2+)versus 2 H(+) for DMDBMA or versus C(1)-C(4) -im(+) and H(+) for FIL-MA at low acidic values, and through anion exchange of [UO(2)(NO(3))(3)](-)versus Tf(2)N(-) for both ligands at high HNO(3) concentrations. The FIL-MA molecule is more efficient than its classical DMDBMA parent.     

Band gaps and structural properties of graphene halides and their derivates: a hybrid functional study with localized orbital basis sets

Density functional theory calculations of the electronic structure of graphane and stoichiometrically halogenated graphene derivatives (fluorographene and other analogous graphene halides) show: (i) localized orbital basis sets can be successfully and effectively used for such two-dimensional materials; (ii) several functionals predict that the band gap of graphane is greater than that of fluorographene, whereas HSE06 gives the opposite trend; (iii) HSE06 functional predicts quite good values of band gaps with respect to benchmark theoretical and experimental data; (iv) the zero band gap of graphene is opened by hydrogenation and halogenation and strongly depends on the chemical composition of mixed graphene halides; (v) the stability of graphene halides decreases sharply with increasing size of the halogen atom--fluorographene is stable, whereas graphene iodide spontaneously decomposes. In terms of band gap and stability, the C(2)FBr and C(2)HBr derivatives seem to be promising materials, e.g., for (opto)electronics applications, because their band gaps are similar to those of conventional semiconductors, and they are expected to be stable under ambient conditions. The results indicate that other fluorinated compounds (C(a)H(b)F(c) and C(a)F(b)Y(c), Y = Cl, Br, I) are stable insulators.     

Iterative operations on microdroplets and continuous monitoring of processes within them; determination of solubility diagrams of proteins

We demonstrate a technique for controlling the content of multiple microdroplets in time. We use this system to rapidly and quantiatively determine the solubility diagrams of two model proteins (lysozyme and ribonuclease A).     

A comparison of two-component and four-component approaches for calculations of spin-spin coupling constants and NMR shielding constants of transition metal cyanides

Relativistic density functional theory (DFT) calculations of nuclear spin-spin coupling constants and shielding constants have been performed for selected transition metal (11th and 12th group of periodic table) and thallium cyanides. The calculations have been carried out using zeroth-order regular approximation (ZORA) Hamiltonian and four-component Dirac-Kohn-Sham (DKS) theory with different nonrelativistic exchange-correlation functionals. Two recent approaches for representing the magnetic balance (MB) between the large and small components of four-component spinors, namely, mDKS-RMB and sMB, have been employed for shielding tensor calculations and their results have been compared. Relativistic effects have also been analysed in terms of scalar and spin-orbit contributions at the two-component level of theory, including discussion of heavy-atom-on-light-atom effects for (1)J(CN), σ(C), and σ(N). The results for molecules containing metals from 4th row of periodic table show that relativistic effects for them are small (especially for spin-spin coupling constants). The biggest effects are observed for the 6th row where nonrelativistic theory reproduces only about 50%-70% of the two-component ZORA results for (1)J(MeC) and about 75% for heavy metal shielding constants. It is important to employ a full Dirac picture for calculations of heavy metal shielding constants, since ZORA reproduces only 75%-90% of the DKS results. Smaller discrepancies between ZORA-DFT and DKS are observed for nuclear spin-spin coupling constants. No significant differences are observed between the results obtained using mDKS-RMB and sMB approaches for magnetic balance in four-component calculations of the shielding constants.     

The Simple Synthesis of Chiral Polyazaoxacoronands Derived from α-Amino Acids

Abstract

Bisamidation of oxaloyl chloride using L-amino acid methyl ester hydrochlorides afforded chiral diesters. The following reactions of diesters with 2,2-(ethylene-dioxy)diethylamine, afforded tetramides possessing C₂ symmetry. Coupling of N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine with 1,5-diamino-3-oxapentane, followed by cleavage of protecting groups, afforded an optically active diamine, which was transformed consequently into tetramide via the reaction with diglycolic acid dimethyl ester under high pressure conditions.     

Formation of ti(28) ln cages, the highest nuclearity polyoxotitanates (ln=la, ce)

The solvothermal reactions of Ti(OEt)(4) with LnCl(3) (Ln=La, Ce) produced new Ti(28) Ln cages, in which the Ln(3+) ions are coordinated within a metallocrown arrangement, which represents the highest nuclearity cages of this type.     

Enantioselective Reformatsky reaction of ethyl iododifluoroacetate with ketones

Two approaches have been developed for the enantioselective Reformatsky reaction of ethyl iododifluoroacetate with ketones to form a quaternary carbon centre using (1R,2S)-1-phenyl-2-(1-pyrrolidinyl)-1-propanol as the chiral ligand. Good yields and high enantioselectivities (80-91% ee) were achieved with a range of alkyl aryl ketones in a convenient one-pot protocol using ethyl iododifluoroacetate and diethylzinc to form the difluorinated Reformatsky reagent homogeneously. In the traditional two-step Reformatsky reaction using the preformed Reformatsky reagent generated from ethyl iododifluoroacetate and zinc dust, good yields and good enantioselectivities (75-84% ee) were also obtained.     

Measured and calculated oxidation potentials of 1-X-12-Y-CB11Me10- anions

Cyclic voltammetry of 31 icosahedral carborane anions 1-X-12-Y-CB(11)Me(10)(-) at a Pt electrode in liquid SO(2) revealed a completely reversible one-electron oxidation even at low scan rates, except for the anions with Y = I, which are oxidized irreversibly up to a scan rate of 5.0 V/s, and the anion with X = COOH and Y = H, whose oxidation is irreversible at scan rates below 1.0 V/s. Relative reversible oxidation potentials agree well with RI-B3LYP/TZVPP,COSMO and significantly less well with RI-BP86/TZVPP,COSMO or RI-HF/TZVPP,COSMO calculated adiabatic electron detachment energies. Correlations with HOMO energies of the anions are nearly as good, even though the oxidized forms are subject to considerable Jahn-Teller distortion. Except for the anion with X = F and Y = Me, the oxidation potentials vary linearly with substituent σ(p) Hammett constants. The slopes (reaction constants) are ~0.31 and ~0.55 V for positions 1 and 12, respectively.     

A general electron transfer reduction of lactones using SmI2-H2O

Herein we describe a strategy for the selective, electron transfer reduction of lactones of all ring sizes and topologies using SmI(2)-H(2)O and a Lewis base to tune the redox properties of the complex. The current protocol permits instantaneous reduction of lactones to the corresponding diols in excellent yields, under mild reaction conditions and with useful chemoselectivity. We demonstrate the broad utility of this transformation through the reduction of complex lactones and sensitive drug-like molecules. Sequential electron transfer reactions and syntheses of deuterated diols are also described.