17O NMR chemical shifts versus structure relationships in oxiranes

Natural-abundance ¹⁷O NMR spectra have been measured for twenty one oxiranes. Their chemical shifts covering a 100 ppm range were interpreted in terms of the paramagnetic β- and diamagnetic γ-effects. In addition, through-space orbital interaction between the ethylenic π and the Walsh orbitals of the oxirane ring was suggested by a lowfield shift in norbornadiene $\text{exo}$-oxide.     

Structure-activity relationships of neuromedin U. V. study on the stability of porcine neuromedin U-8 at the C-terminal asparagine amide under mild alkaline and acidic conditions

Porcine neuromedin U-8 (X-Asn-NH(2), X=H-Tyr-Phe-Leu-Phe-Arg-Pro-Arg) is occasionally unstable in the biological fluids used for bioassay as well as in the acidic solutions used for purification of synthetic peptides. In this study, HPLC examination of an incubate solution of X-Asn-NH(2) revealed that the main decomposition products in Tyrode's solution (pH 7.4) were either alpha- or beta-monocarboxylic acid analogs (X-Asn-OH or X-Asp-NH(2)), and that no dicarboxylic acid analog (X-Asp-OH) was produced. Further investigation, employing a model peptide (Y-Asn-NH(2), Y=Benzoyl-Pro-Arg) incubated in a 0.1 M sodium bicarbonate solution at 60 degrees C, revealed that the decomposition of C-terminal Asn-NH(2) occurred through the formation of an aminosuccinimide intermediate (Y-Asu), at a rate faster than that of Y-Asn-Ser peptide but slower than that of Y-Asn-Gly peptide. Mild acid hydrolysis of X-Asn-NH(2) examined in a 1 M HCl solution at 60 degrees C yielded X-Asn-OH and X-Asp-NH(2), which further decomposed to yield X-Asp-OH. The C-terminal degradation of X-Asn-NH(2) resulted in reduced biological and immunochemical binding activities.     

Hyperspaces of Normed Linear Spaces with the Attouch–Wets Topology

Let Cld _AW (X) be the hyperspace of nonempty closed subsets of a normed linear space X with the Attouch–Wets topology. It is shown that the space Cld _AW (X) and its various subspaces are AR's. Moreover, if X is an infinite-dimensional Banach space with weight w(X) then Cld _AW (X) is homeomorphic to a Hilbert space with weight 2 ^w(X).     

Fluorine-containing amino acids and their derivatives. 6. An efficient synthesis of β-fluorinated alanines via fluorohalomethylation of aminomalonates

Aminomalonates, e.g., $\text{1}$ and $\text{2}$, smoothly reacted with difluoro- and chlorofluorocarbene to produce the adducts ($\text{3}$, $\text{4}$, and $\text{5}$) in good yields. These products were successfully converted to various versatile β-fluorinated alanine derivatives, i.e., β,β-difluoroalanine ($\text{6}$), N-acyl-β-fluorodehydroalaninate ($\text{7}$), and fluoropyruvic acid ($\text{8}$).     

Preparation of 4-hydroxy-2-alkenenitriles from phrnylsulfinylacetonitrile with keetones or aldehydes,and its synthetic application to substituted furans

The reaction of phenylsulfinylacetonitrile 1 with ketones or aldehydes gave 4-hydroxy-2-alkenenitriles which were converted to 2- and/or 3-substituted furans by the treatment with diisobutylaluminumhydride(DIBAL) followed by acid hydrolysis.     

Swern Oxidation of α-Ketols to α-Diketones1

The Swern oxidation of acyclic and cyclic α-ketols delivered α-diketones or the tautomeric diosphenols in good yield.