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.     

A convenient method for the preparation of α-vinylfurans by phosphine-initiated reactions of various substituted enynes bearing a carbonyl group with aldehydes

α-Vinylfurans were obtained by phosphine-initiated cyclization of various enynes bearing a carbonyl group at the ene end in the presence of various aldehydes, in moderate to high yields. The reaction may consist of 1,6-addition of phosphine to the enynes, ring closure, and Wittig reaction between the ylid resulting from cyclization and an aldehyde. Thus, various aldehydes were able to be used in the reaction. The reaction was influenced greatly by the substituents at the acetylene position (R¹) and the α-position of the carbonyl group (R³).     

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.     

Hydroformylation in fluorous solvents

The hydroformylation of long chain alkenes under fluorous biphase conditions and in neat perfluorocarbon solvents is reviewed. Special emphasis is placed upon the authors' evaluation of the steric and electronic influence of perfluoroalkylation on catalyst activity, regioselectivity and retention in the fluorocarbon phase.     

Synthesis and stereochemical studies of di and tetra 9,9′-spirobifluorene porphyrins: new building blocks for catalytic material

We report the synthesis and stereochemical properties of a new class of molecules containing a covalently-linked porphyrin and spiro-9,9′-bifluorene derivatives. The large spiro substituents hinder rotation about the meso position to give atropisomers which can be detected by ¹H NMR after phosphine or isocyanide complexation to the ruthenium spiroporphyrins.     

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.     

镍 钴 钯 铁2—（二苯基膦基）吡啶配合物的合成及其催化羰基化反应

众所周知,铑催化剂是醇类羰基化的有效催化剂,但是铑价格昂贵且对设备有腐蚀性,因此,寻找出对醇类羰基化催化活性好的非贵金属催化剂,对醇类羰化的工业化有十分重要的意义。 本文在温和条件下,合成了四种含有相同配体(Ph_2PPy)不同金属的有机配合物(金属基分别为Ni、Co、Pd、Fe),并探索了它们对乙醇羰基化反应的催化活性。     

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。