Enantioselective spiro ene-carbocyclization of 1,6-enynes catalyzed by tropos rhodium(I) complex with skewphos ligand

A tropos rhodium(I) complex having skewphos ligand is shown to be a highly enantioselective catalyst for asymmetric ene-type carbocyclization of 1,6-enynes with tri-substituted olefins to control quaternary stereogenic centers or spiro-rings.     

Radical addition to vinyl sulphones and vinyl phosphonium salts

Alkyl radicals, derived from decarboxylation of carboxylic acids, add readily to phenyl vinyl sulphone and vinyl phosphonium bromide. The adducts may be further converted into a variety of useful synthetic intermediates.     

Efficient esterification of carboxylic acids and phosphonic acids with trialkyl orthoacetate in ionic liquid

An operationally simple, inexpensive, efficient, and environmentally friendly esterification of various carboxylic acids, phosphonic acids, and phosphinic acids with triethyl orthoacetate or trimethyl orthoacetate under neutral conditions in a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was successfully carried out to provide the corresponding ethyl esters or methyl esters in high yields.     

A multipolymer system for organocatalytic alcohol oxidation

A system involving two polymer-supported reagents for the selective and organocatalytic oxidation of alcohols to aldehydes or ketones has been developed in which both polymeric reagents can be recovered and reused.     

A highly diastereoselective pinacol coupling reaction of aldehydes and ketones using low-valence niobium generated from Nb(V)

A simple method for the diastereoselective synthesis of racemic 1,2-diol mediated by low-valence niobium generated in situ is described. A 1,4-dioxane-toluene solvent system was found to be essential to achieve higher selectivities and to prevent other reactions of pinacols, such as deoxygenation and acetal formation. Aromatic aldehydes and ketones were converted to the corresponding pinacols with up to 97 and 85% de, respectively.     

Synthesis of calix[4]arene library substituted with peptides at the upper rim

A fluorescence-labeled calix[4]arene library substituted with peptides at the upper rim was synthesized. Screening of the library for binding a dye-labeled oligopeptide indicated that some peptidocalix[4]arenes selectively bind the oligopeptide. The chemosensitivity of the library members for a target peptide was also investigated.     

Iodophosphoryloxylation of carbon-carbon multibonds and its application to glycals

Iodophosphoryloxylation of carbon-carbon multibonds was attempted. Alkynes and cyclohexene were converted to the corresponding 1,2-iodophosphoryloxylated compounds in moderate to good yields with a trivalent iodine compound/iodine system, while glucal gave mainly the corresponding iodohydrin compound in this system. However, 2-deoxy-2-iodoglycosyl diphenylphosphinates were obtained from the corresponding glycals with a diphenylphosphinic acid/iodine/potassium carbonate system in good yields. Moreover, triethylborane smoothly reduced 2-deoxy-2-iodoglycosyl diphenylphosphinates to 2-deoxyglycosyl diphenylphosphinates in a 1,4-cyclohexadiene solvent.