Y. Inamoto

A convenient synthesis of long-chain 1-O-Alkyl glyceryl ethers

A convenient and economical procedure for synthesis of long-chain 1-O-alkyl glyceryl ethers (V) is described. Alkyl glycidyl ethers (II) which were derived from the reaction of alcohols (I) with epichlorohydrin using a phase transfer catalyst were first converted into the corresponding dioxolanes (III) or 1-O-alkyl-2,3-di-O-acetylglycerols (IV). Subsequent hydrolysis of the resultant products provided 1-O-alkyl glyceryl ethers (V) in high yields.

Hydrogenation of carboxylic acids by rhenium-osmium bimetallic catalyst

Hydrogenation of carboxylic acids to alcohols at low temperature and under low pressure was achieved by using a new catalyst system, a rhenium-osmium bimetallic catalyst. The most active catalyst was prepared by the reductionof the corresponding metal oxides with hydrogen in the presence of succinic acid. Decanoic acid was hydrogenated to decanol in high conversions at 25∼100 atm and 100∼120°C. Decane was formed as a by-product by overreduction of the alcohol. The selectivity of alcohol was improved by the addition of thiophene as a modifier of the catalyst.

Novel fluoride transfer in the reaction of tricyclic epoxides with boron trifluoride

Abstract Reaction of the tricyclic epoxides ( 1a ) and ( 1b ) with boron trifluoride etherate leads to fluorohydrins ( 2a ) and ( 2b ) derived in the novel fluoride transfer, whereas ( 1c ) undergoes isomerization to spiro ketone ( 3 ).

Palladium-catalyzed acylation of activated alkenes with bridgehead acid chlorides

Abstract Bridgehead acid chlorides 1a and 1b react with activated alkenes 2 in the presence of a catalytic amount of palladium and 1 equiv of a tertiary amine. The reaction proceeds regio- and stereoselectively at the terminal carbon atoms to yield acylated alkenes 3 with E-configuration.

Palladium-catalyzed decarbonylation of tricyclic bridgehead acid chlorides

Abstract Decarbonylation of tricyclic bridgehead acid chlorides 1 and 4 with palladium catalyst in the presence of tri- n -butylamine proceeded at 130 °C to give exclusively stable disubstituted olefins 3 and 6 , with probable intermediacy of the bridgehead olefins 2 and 5 , respectively.

A Convenient Synthesis of 4-Homoisotwistane

Abstract Tricyclo[5.3.1.03,8] undecane (II), which would be conveniently refered to by the trivial name 4-homoisotwistane in accordance with Majerskis nomenclature,1 was first prepared by Krantz2 during the stereoselectivity study on intramolecular Diels-Alder reactions of 5-alkenylcyclohexa-1,3-dienes, and recently discovered independently by Schleyer,3 Majerski1 and us4 to be involved as a reasonably stable intermediate in acid-catalyzed isomerization of various tricycloundecane precursors to equilibrium mixtures of 1 and 2-methyladamantanes.

New Synthesis of Mono-Halogenated Adamantanes

Abstract A variety of direct halogenations on the adamantane skeleton have been reported. For example, bromination of adamantane with bromine, which is considered to proceed through an ionic mechanism, gives high yield of 1-broinoadamsntane. In contrast to the ionic bromination of adamantane, chlorinations are much less selective2,3,4,5. Photochloroadamantane of adamantane gives l-chloroadamntane and 2-chloroadamantane. Chlorination with t-butyl chloride in the presence of A1C13 gives rise to a mixture of 1-chloroadamantane and 1,3-dichloroadamantane.

Ready formation of a Bredt compound, tricyclo[5,3,1,03,8]undec-2-ene. conformational preference leading to regiospecificity in a planar cis-elimination

Dehydrobromination of 3,9-ethanobicyclo[3,3,1]-non-l-yl (tricyclo[5,3,1,03,8]undec-3-yl) bromide (I) with sodium amide in refluxing toluence gave 3,9-ethanobicyclo[3,3,1]non-1-ene (tricyclo[5,3,1,03,8]undec-2-ene)(II) in 52% yield.