Alkene substituents for selective activation of endo-regioselective polyepoxide oxacyclizations

The presence of an alkenyl substituent on the terminal epoxide of a polyepoxide substrate enhances the yield of all-endo-regioselective tandem oxacyclization to trans-syn-trans-fused polycyclic ethers. For a substrate in which the epoxide and alkene functional groups are separated by two methylene substituents, a novel bromonium ion-induced endo-regioselective cyclization to bromooxepane is also described. [reaction: see text]     

Aminooxazolinate; a chiral amidinate analogue

High levels of diastereoselection with respect to chirality-at-metal are achieved at equilibrium for complexes containing a new and available range of diazaallyl ligands.     

Yttrium polyoxometalates. Synthesis and characterization of a carbonate-encapsulated sandwich-type complex

Reaction of A-alpha-PW(9)O(34)(9)(-) with YCl(3) in an aqueous Na(2)CO(3) solution produces a dianion-encapsulated A-type sandwich polyoxometalate, (YOH(2))(3)(CO(3))(A-alpha-PW(9)O(34))(2)(11)(-). The X-ray structure of this complex reveals that three Y(III) ions are sandwiched between two A-alpha-PW(9)O(34)(9)(-) moieties and that a carbonate dianion is encapsulated in the same plane as the three Y(III) atoms. The oxygen atoms of the CO(3)(2)(-) are sitting at the midpoints of the sides of the triangle formed by the three Y(III) ions. (31)P and (13)C NMR studies confirm that this complex is significantly more stable than the analogous A-type sandwich polyoxometalates containing divalent metals.     

A new copper acetate-bis(oxazoline)-catalyzed, enantioselective Henry reaction

A highly enantioselective, nitroaldol reaction catalyzed by a chiral Cu(II) bis(oxazoline) complex has been developed. The reaction scope includes both aromatic and aliphatic aldehydes (15 examples) affording products in good yields and enantioselectivities (87-94% ee). An X-ray structure of the catalyst has been provided along with a rationalization of the sense of asymmetric induction.     

Maximum norm stability of difference schemes for parabolic equations on overset nonmatching space-time grids

In this paper, theoretical results are described on the maximum norm stability and accuracy of finite difference discretizations of parabolic equations on overset nonmatching space-time grids. We consider parabolic equations containing a linear reaction term on a space-time domain which is decomposed into an overlapping collection of cylindrical subregions of the form , for . Each of the space-time domains are assumed to be independently grided (in parallel) according to the local geometry and space-time regularity of the solution, yielding space-time grids with mesh parameters and . In particular, the different space-time grids need not match on the regions of overlap, and the time steps can differ from one grid to the next. We discretize the parabolic equation on each local grid by employing an explicit or implicit -scheme in time and a finite difference scheme in space satisfying a discrete maximum principle. The local discretizations are coupled together, without the use of Lagrange multipliers, by requiring the boundary values on each space-time grid to match a suitable interpolation of the solution on adjacent grids. The resulting global discretization yields a large system of coupled equations which can be solved by a parallel Schwarz iterative procedure requiring some communication between adjacent subregions. Our analysis employs a contraction mapping argument.

Applications of the results are briefly indicated for reaction-diffusion equations with contractive terms and heterogeneous hyperbolic-parabolic approximations of parabolic equations.

     

Poly(4-vinylpyridine) catalyzed hydrolysis of methyl bromide to methanol and dimethyl ether

The hydrolysis of methyl bromide with neutral water is performed in the presence and absence of various amines in a batch reactor at different temperatures (50–125 °C). Screening of poly(4-vinylpyridine) as a potential reusable solid amine catalyst showed maximum efficiency. This significant enhancement in efficiency is due to the capture of HBr by solid PVP and remains phase-separated driving the reaction forward. The major advantage of this process is that the polymer can be easily regenerated and reused without loss of activity making it a very effective catalyst for the conversion of methyl halides to methanol and dimethyl ether.     

Acid-catalyzed isomerization of pivalaldehyde to methyl isopropyl ketone via a reactive protosolvated carboxonium ion intermediate.

Quantitative rearrangement of pivalaldehyde to methyl isopropyl ketone is observed in acids such as trifluoromethanesulfonic acid, anhydrous HF, and trifluoroethyl alcohol-BF3 but not in trifluoroacetic acid. Studies in a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid show that acids with H(o) < or = -11 are able to carry out complete isomerization. These results and density functional theory calculations at the B3LYP/6-31G level suggest that protonated pivalaldehyde undergoes further protosolvation at higher acidities to a reactive superelectrophilic species resulting in rearrangement. A mechanism for the pivalaldehyde rearrangement to methyl isopropyl ketone in strong protic acids involving a reactive protosolvated superelectrophilic intermediate is suggested. Aspects of the related mechanism of the reaction with isobutane with CO in HF/BF3 medium leading to methyl isopropyl ketone are also discussed.     

Compounds of arsenic,antimony, and tin in mollusc shells

Inorganic arsenic(III) and arsenic(V), methyl-arsenicals, antimony(III), and antimony(V), and butyltin derivatives are present in the shells of molluscs found in the coastal waters of British Columbia.     

A comparison of rigid and flexible crosslinked polymer-supported peptide synthesis

To correlate the coupling difficulty and nature of the support in solid-phase peptide synthesis, a set of difficult peptides were built under identical conditions on rigid and hydrophobic divinyl benzene-crosslinked polystyrene (DVB-PS) and flexible and polar 1,4-butanediol dimethacrylate-crosslinked polystyrene (BDDMA-PS) resins of same functional capacity (∼2 mmol/g). The difficult coupling stages observed on each support were identified by monitoring the acylation time, coupling yield and deprotection efficiency. The yield and purity of the peptides prepared on BDDMA-PS were higher than when DVB-PS support was used.