A Hydroperoxide-Mediated Decarboxylation of α-Ketoacids Enables the Chemoselective Acylation of Amines

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information.     

Radiolytic unsaturation decay in polyethylene. Part III—the effect of certain chain transfer agents

Small amounts of certain halogenated compounds are found to have, at most, only a slight enhancing effect on the radiolytic decay rates of added poly-unsaturated compounds in polyethylene, but significantly increase the elastic modulus at 433 K (melt modulus) obtained thereby. Experiments with model chlorine-containing additives suggest that this increase is due to a more random distribution of polymer and monomer mediated crosslinks in the polymer, that it does not result from a significant increase in crosslinking and that it is mediated by chlorine atoms, in a similar manner to radiolytic hydrogen atoms, through facilitation of long range free radical migration. Although low molecular weight chloro-paraffins inhibit radiolytically induced growth of melt modulus in monomer containing polyethylenes, even very small additions of chlorinated polyethylenes, which form a separate phase, increase the melt modulus. This again indicates that the active species is the chlorine radical.     

Cinnamic acid amides and lignanamides from Aptenia cordifolia

Examination of the hydroalcoholic extract of the leaves of Aptenia cordifolia has afforded three cinnamic acid amides and two lignanamides. Structures were established on the basis of spectroscopic data, including 2D-NMR analyses.     

Preparation of a new hydrophilic copolymer from a polylactone and the structure analyses

A new hydrophilic copolymer having three kinds of hydroxyl groups, i.e. primary OH on -hydroxy allyl alcohol component, secondary OH on cyclic hemiacetal component and tertiary OH on -hydroxy acrylate component, was prepared by reducing a ‘polylactone’, poly(1-oxa-2-oxobutane-1,4:3,3-tetrayl), with NaBH₄ in mixed solvents containing an alcohol. The structural analyses were performed by the solution ¹H NMR and the solid state ¹³C NMR spectroscopies of the reduced samples. The composition of the three components turned out to be variable to the alcohol species used for the mixed solvent.     

New 6-Arylsulfonyl-1,2-benzoisothiazol-3(2H)-one 1,1-Dioxides Derived from Diphenyl Sulfone Monosulfonyl Chlorides

Various methods were studied for the oxidation of 2-methyl-5-(phenylsulfonyl)benzenesulfamide and its derivatives. The oxidation by sodium dichromate in sulfuric acid was found most efficient. The effects of temperature, concentration, reagent ratio, and time of the oxidation reaction on the yield of the desired product were investigated. Conditions were proposed for obtaining the desired product in yields up to 95%. A synthesis was developed for a series of new saccharin derivatives.     

羧酸直接酰胺化的一个新方法

N, N-二甲基取代酰胺可以方便地由脂肪族或芳香羧酸与四(二甲氨基)硅烷在无水溶剂中反应制得。     

烯丙基碘和锡与醛的选择加成反应

含活性基团的醛可与烯丙碘和锡粉直接进行亲核加成反应，得到高烯丙基的醇，水的存在不利于此反应的进行，与烯丙基溴相比，烯丙基碘反应活性更强，可在短时间内得较高的产率。