Preparation of multisubstituted allenes from allylsilanes

[reaction: see text] A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KO(t)Bu, afforded substituted 2-bromo-1,3-butadienes with elimination of bromosilanes. The Pd-catalyzed reaction of the bromodienes with soft nucleophiles gave the allene derivatives. Previously inaccessible tri- and tetrasubstituted allenes can be prepared by this method as well.     

Unprecedented double C-C bond cleavage of a cyclopentadienyl ligand

Double C-C bond cleavage of a cyclopentadienyl ligand proceeded to titanacyclopentadienes when 2 equiv of nitriles were added and the resulting two-carbon unit and three-carbon unit were converted into a benzene derivative and a pyridine derivative, respectively, in one-pot.     

Direct conversion of allylic alcohols into N-acyl-α-amino acids by catalytic amidocarbonylation by means of homogeneous binary systems

N-Acyl-α-amino acids are synthesized by the amidocarbonylation of allylic alcohols catalyzed by homogeneous binary systems which consist of cobalt carbonyl and rhodium (or iron or palladium) complexes.     

1,3,8,10-Tetrahydro-2,9-diazadibenzo[cd,lm]perylenes: synthesis of reduced perylene bisimide analogues

A unique family of 1,3,8,10-tetrahydro-2,9-diazadibenzo[cd,lm]perylenes (THDAP) was prepared through a new synthetic strategy. Completion of the synthesis was achieved in several steps from commercially available perylene-3,4,9,10-tetracarboxylic dianhydride via reactions between 3,4,9,10-tetra(chloromethyl)perylene and primary amines. The successful use of a variety of primary amines in the reactions indicated that the synthetic approach provides a rich opportunity to produce new functionalized perylene derivatives.     

A Novel Production of γ-Butyrolactone Catalyzed by Homogeneous Ruthenium Complexes

γ-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity.     

Reaction of sulphoximides with diazomalonate in the presence of Cu-salt : A new synthesis and stereochemistry of optically active oxosulphonium ylides

Sulphoximides (Ia–Ie) were found to react with dimethyl diazomalonate (DDM) in the presence of a catalytic amount of Cu-salts affording the corresponding oxosulphonium ylides in moderate yields. The reaction did not proceed at all under irradiation of UV light. (?)-Methylphenyloxosulphonium bis(methoxycarbonyl)-methylide ((?)-IIb) was obtained from (+)-(S)-methylphenylsulphoximide ((+)-(S)-Ib) together with (?)-(S)-methyl phenyl sulphoxide ((?)-(S)-IIIb) by this reaction. Hydrolysis of (?)-IIb gave (+)-methylphenyloxosulphonium methoxycarbonylmethylide ((+)-IIf) which was converted to (?)-(S)-IIIb upon treatment with dibenzoylethylene. Stereochemical cycle starting from (+)-(S)-Ib to (?)-(S)-IIIb was established and the absolute configurations of both ylides, (?)-IIb and (+)-IIf were assigned as (R)-configuration. The stereochemical courses, namely from (+)-(S)-Ib or (?)-(S)-IIIb to (?)-(R)-IIb or (+)-(R)-IIf to (?)-(S)-IIIb were determined as retention processes. The optical purities of the oxosulphonium ylides obtained from both reactions, (+)-(S)-Ib→(?)-(R)-IIb and (?)-(S)-IIIb→(?)-(R)-IIb, were almost equal. These results indicate that the mechanism of the reaction of sulphoximides with carbenes (or carbenoids) involves the initial formation of the sulphoxides which react subsequently with carbenes to afford the final products.     

Crystal structure of poly(p-benzamide)

Redetermination of the crystal structure of poly(p-benzamide) was made by using newly collected intensity data. The molecular conformation is TCTC, where the internal rotation angles about the N? C bond of the amide group and about the virtual bond of N-phenyl-C are T (trans) and C (cis) conformations, respectively. Two molecular chains pass through a rectangular unit cell with dimension, a = 7.75 Å, b = 5.30 Å, c (fiber axis) = 12.87 Å, and the space group, P2₁2₁2₁-D. The reflection observed at the spacing of 010 may be attributed to the reflection due to another crystal polymorph or the diffuse scattering due to disorder. © 1993 John Wiley & Sons, Inc.     

A novel method for preparation of 2-(methyl- or phehnylthio)alkanoic esters

Ethyl 2-acetylalkanoate gave ethyl 2-(methyl- or phenylthio)alkanoate in high yield on treatment wiht CH₃SSO₂CH₃, PhSSO₂Ph, or PhSSPh in the presence of small excess of EtONa in EtOH. Application of the present method to synthesis of pellitorine and the queen substance is also described.