Diastereoselective addition of vinylmagnesium halides to variously N-mono- and N,N-diprotected l-alaninals

Diastereoselective C₂-elongation processes of N-mono- 1a-c and N,N-diprotected 1d-fl-alaninals, using vinylmagnesium bromide and chloride, are described. A substantial difference between effects of the N-protecting groups replacing either one or two amino protons was observed.     

Effective High‐Pressure Cleavage of Sterically Hindered Steroid Esters

A simple and effective method to deprotect of sterically hindered steroid esters is described. Deprotection was carried out in MeOH in the presence of a catalytic amount of Et₃N under high‐pressure conditions. Enzymatic, anionite, and high‐pressure methods are compared.     

Polyester oligodiols by cationic AM copolymerization of L,L‐lactide and ε‐caprolactone initiated by diols

Cationic copolymerization of L,L ‐lactide (LA) and ε‐caprolactone (CL) initiated by low molecular weight diols in the presence of acid catalyst gives corresponding copolyesters terminated at both ends with hydroxyl groups in practically quantitative yield. Copolymerization proceeds by Activated Monomer mechanism. LA is consumed preferentially and at the later stages of copolymerization the reaction mixture is enriched with CL. In spite of that, random distribution of both units is observed and end‐groups are mainly ? LA‐OH groups and not ? CL‐OH groups. This is explained by the fact that to reach high conversion of both comonomers the relatively long reaction times are required and at those conditions transesterification reaction becomes significant. Thus the microstructure of copolymers and the nature of the end‐groups is governed by transesterification rather then by the kinetics of comonomers incorporation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3090–3097, 2007     

Diastereomeric non-equivalence of (−)-ω-camphanic esters of chiral secondary alcohols in 13C NMR spectroscopy

The diastereomeric differences (Δδ) were measured by ¹³C NMR spectroscopy for a series of 11 (?)-ω-camphanic esters of secondary alcohols of known absolute configuration. This method cannot be used for the determination of the absolute configuration, but it can be applied to the estimation of the enantiomeric purity of chiral alcohols.     

Synthesis and structure of a 1:1 complex of a chiral methyl 4,6-0-benzylidene-2 , 3-0 (1 ,2-bis (ethoxyethoxy) -benzenediyl) - α,d-glucopyranoside and potassium iodide

The chiral crown ether was prepared according to the method described in the literature and its complex with potassium iodide was obtained. The crystal data are as follows: a = 10.315(4), b = 9.265(4), c = 15.88(2) Å, β = 100.70(7)°. V = 1494 Å,³ Z = 2, D₀ = 1.55 Mg m^?3 space group symmetry P2₁.The structure was determined by the heavy atom method using 2214 independent observed reflections. The conformation of the macrocyclic ring is discussed.     

Single-shot extreme ultraviolet laser imaging of nanostructures with wavelength resolution

We have demonstrated near-wavelength resolution microscopy in the extreme ultraviolet. Images of 50 nm diameter nanotubes were obtained with a single ~1 ns duration pulse from a desktop-size 46.9 nm laser. We measured the modulation transfer function of the microscope for three different numerical aperture zone plate objectives, demonstrating that 54 nm half-period structures can be resolved. The combination of near-wavelength spatial resolution and high temporal resolution opens myriad opportunities in imaging, such as the ability to directly investigate dynamics of nanoscale structures.     

Synthesis,crystal and molecular structures of 1,8-diaza-11,14-dioxacyclohexadeca-2,7-dione and 1,10-diaza-4,7-dioxacyclohexadeca-2,9-dione

1,8-Diaza-11,14-dioxacyclohexadeca-2,7-dione (3) has been synthesized under high-pressure conditions, whereas 1,10-diaza-4,7-dioxacyclohexadeca-2,9-dione (6) has been obtained under thermal conditions. Both compounds have been investigated in the solid state and in solution by X-ray structural and NMR methods, respectively. The crystals of3 are orthorhombic, space groupPbca; the crystals of6 are triclinic, space groupP¯1. Both structures were solved by direct methods, and refined by a full-matrix, least-squares procedure giving for3 R=0.045 and for 6R=0.056 (R _w =0.065). From the NMR investigations in solution a twofold symmetry of both molecules (probably in intermediate conformations) is suggested; no such symmetry was found in crystalline state. The structure of6 exhibits a positional disorder of one O-heteroatoms with the population ratio 0.510.49. The arrangement of the macroring with respect to the carbonyl groups was found to betransoid in3 andcisoid in6.     

Greedy wavelet projections are bounded on BV

Let be the space of functions of bounded variation on with . Let , , be a wavelet system of compactly supported functions normalized in , i.e., , . Each has a unique wavelet expansion with convergence in . If is the set of indicies for which are largest (with ties handled in an arbitrary way), then is called a greedy approximation to . It is shown that with a constant independent of . This answers in the affirmative a conjecture of Meyer (2001).

     

Copolyethers with controlled structure: Mechanism of formation and microstructure

Cationic copolymerization of 3-membered cyclic ethers (oxiranes) with 5-membered cyclic ether (tetrahydrofuran) leads to linear copolyethers containing significant amount of cyclic fraction. When the copolymerization is conducted in the presence of diols, telechelic copolymers are formed by the process in which oxirane is incorporated into copolymer irreversibly by Activated Monomer mechanism, while tetrahydrofuran is incorporated reversibly by Active Chain End mechanism. Thus both kinetic and thermodynamic factors can be used to control the rate of the incorporation of comonomers. Studies of the kinetics of the competing reactions leading to formation of copolymer, studies of copolymer microstructure by ¹³C-NMR and analysis of the composition of the cyclic fraction, led to the correlation between the copolymer microstructure and the amount of cyclic fraction formed. The dependence of the cyclic fraction content on the reaction conditions was therefore explained.