Synthesis of enantiopure 3-azabicyclo[3.3.0]octen-7-one derivatives via intramolecular Pauson-Khand cycloaddition reaction using tri-O-acetyl-D-glucal as starting material

Some N-substituted-3-azabicyclo[3.3.0]octen-7-one derivatives have been synthesized in an enantiomerically pure form starting from tri-O-acetyl-D-glucal via intramolecular Pauson-Khand (IPK) cycloaddition.     

Interpolation by Polynomials and Radial Basis Functions on Spheres

The paper obtains error estimates for approximation by radial basis functions on the sphere. The approximations are generated by interpolation at scattered points on the sphere. The estimate is given in terms of the appropriate power of the fill distance for the interpolation points, in a similar manner to the estimates for interpolation in Euclidean space. A fundamental ingredient of our work is an estimate for the Lebesgue constant associated with certain interpolation processes by spherical harmonics. These interpolation processes take place in ``spherical caps' whose size is controlled by the fill distance, and the important aim is to keep the relevant Lebesgue constant bounded. This result seems to us to be of independent interest. March 27, 1997. Dates revised: March 19, 1998; August 5, 1999. Date accepted: December 15, 1999.     

Crystallographic and Solution Anion Binding Studies of Bis-amidofurans and Thiophenes

A variety of furan and thiophene amide and thioamide cleft type anion receptors have been synthesised and crystallographically characterised. Unlike 2,5-diamidopyrrole anions, analogous 2,5-diamidofurans and thiophenes do not interlock in the solid state. The anion binding properties of these receptors have been investigated in DMSO/0.5% water solution using ¹H NMR titration techniques. Solution studies and solid-state evidence suggests that the thiophene receptors may utilise a thiophene CH hydrogen atom for hydrogen bond formation to anions with a 2,4-diamidothiophene showing similar anion binding affinities to a 2,5-diamidopyrrole.     

REACTIONS OF SULFUR DIOXIDE WITH AMINOPHOSPHINES

Abstract

The reactions of SO₂ with tris-dimethylaminophosphine, bis-dimethylaminofluorophosphine, bis-dimethylaminochlorophosphine, dimethylaminodifluorophosphine, dimethylaminodichlorophosphine, 1,3-dimethyl-2-fluoro-1,3,2-diazaphospholidine and 1,3-dimethyl-2-chloro-1,3,2-diazaphospholidine have been investigated. The complex reactions are dominated by facile oxidation of the respective phosphine to phosphoryl and thiophosphoryl derivatives. The new heterocyclic phosphines CH₃ NCH₂CH₂N(CH₃)P(O)F and CH₃ NCH₂CH₂N(CH₃)P(S)F have been isolated and characterized by NMR, infrared, and mass spectrometry.     

用信息熵描述非线性光传输的研究

结合光束传输的薛定谔形式理论，基于量子机制的信息熵被用来描述非线性光传输，理论推导和数值模拟结果表明：信息熵及其对光传输方向的变化率可以表征光脉冲的压缩或展宽或光束的聚焦与发散，用信息熵表征非线性光传输优于对用脉（束）宽，二阶矩表征。     

1,3-Diindolylureas: high affinity dihydrogen phosphate receptors

Neutral 1,3-di(1H-indol-7-yl)ureas are selective dihydrogen phosphate receptors in polar solvent mixtures (DMSO-d(6)-25% water).     

Stepwise cycloadditions of mesoionic systems: thionation of thioisomünchnones by isothiocyanates

An unusual thionation strategy of mesoionic compounds with aryl isothiocyanates enables a facile synthesis of 1,3-thiazolium-4-thiolate systems. The mechanistic pathway of such a transformation most likely involves a stepwise 1,3-dipolar cycloaddition, which is supported by theoretical calculations performed with a two-layer hybrid method (B3LYP/6-31G(d):PM3).     

Cooperative effect of carborane and pyridine in the reaction of carboranyl alcohols with thionyl chloride: halogenation versus oxidation

Thionyl chloride (SOCl2) acts as halogenation reagent in its reaction with 1-[phenyl(hydroxy)methyl]-2-R-1,2-dicarba-closo-dodecaborane 1a, b but unexpectedly behaves as an oxidant for 1-[2'-pyridyl(hydroxy)methyl]-2-R-1,2-dicarba-closo-dodecaboranes 2a, b. The synthesis and characterization of all new compounds, including structure determinations of 1a, 2a, 1-[phenyl(chloro)methyl]-2-methyl-1,2-dicarba-closo-dodecaborane 3a, and 1-[2'-pyridyl(oxo)methyl]-2-methyl-1,2-dicarba-closo-dodecaboranes 4a are reported and the possible pathways are discussed.     

Chiral N-acyloxazolidines: synthesis, structure, and mechanistic insights

A series of chiral imines derived from 1-amino-1-deoxyalditols such as d-glucamine, a rather unexplored raw material from the chiral pool, have been serendipitiously transformed into a novel family of N-acetyl-1,3-oxazolidines by means of an unexpected acetylation. The structure of these substances is supported by spectroscopic and crystallographic data. The acetylates also trigger a complex dynamic transformation, in which an initially configured trans oxazolidine converts into a more stable cis-configured derivative. Both isomers can also exist as rotational conformers (E,Z) as a consequence of the restricted rotation around the N-acetyl bond. The barriers to rotation have been determined by variable-temperature experiments. Overall, this transformation most likely involves the intermediacy of a chiral iminium ion, which has been documented in the synthesis of nitrogen heterocycles, thus explaining the experimental facts.