A stable silicon-based allene analogue with a formally sp-hybridized silicon atom.

Carbon chemistry exhibits a rich variety in bonding patterns, with homo- or heteronuclear multiple bonds involving sp-hybridized carbon atoms as found in molecules such as acetylenes, nitriles, allenes and carbon dioxide. Carbon's heavier homologues in group 14 of the periodic table--including silicon, germanium and tin--were long thought incapable of forming multiple bonds because of the less effective p(pi)-p(pi) orbital overlap involved in the multiple bonds. However, bulky substituents can protect unsaturated bonds and stabilize compounds with formally sp-hybridized heavy group-14 atoms: stable germanium, tin and lead analogues of acetylene derivatives and a marginally stable tristannaallene have now been reported. However, no stable silicon compounds with formal sp-silicon atoms have been isolated. Evidence for the existence of a persistent disilaacetylene and trapping of transient 2-silaallenes and other X = Si = X' type compounds (X, X' = O, CR2, NR, and so on) are also known, but stable silicon compounds with formally sp-hybridized silicon atoms have not yet been isolated. Here we report the synthesis of a thermally stable, crystalline trisilaallene derivative containing a formally sp-hybridized silicon atom. We find that, in contrast to linear carbon allenes, the trisilaallene is significantly bent. The central silicon in the molecule is dynamically disordered, which we ascribe to ready rotation of the central silicon atom around the molecular axis.

Formation of cyclic ethers via the palladium-catalyzed cycloaddition of activated olefins with allylic carbonates having a hydroxy group at the terminus of the carbon chain.

The reaction of the activated olefins 1 with the allylic carbonate 2, having a hydroxy group at the terminus of the carbon chain, in the presence of catalytic amounts of Pd(2)dba(3).CHCl(3) and dppe in THF at room temperature gave the corresponding cycloaddition products, tetrahydrofuran derivatives 5, in good to very high yields. The diastereoselectivities (trans/cis ratios) of the products were in the range of ca. 60-70/40-30. The reaction of 1 with the hydroxy allylic carbonate 3 in the presence of catalytic amounts of Pd(2)dba(3).CHCl(3) and (o-tolyl)(3)P in THF at 50 degrees C afforded the corresponding cycloaddition products, tetrahydropyran derivatives 6, in good to high yields. The trans/cis ratios of the products were in the range of ca. 0-40/99-80. The reaction of 1a with the hydroxy allylic carbonate 4 needed higher reaction temperatures (approximately 100 degrees C) to give the cycloaddition product, the oxepane 7a, in 31% yield with low diastereoselectivity. Next, catalytic asymmetric syntheses of tetrahydrofuran and -pyran derivatives were carried out. With the Trost ligand 15, good to high ees were accomplished in the cycloaddition, although the diastereoselectivities were of low level. With the Hayashi ligand 16, good to high ees were also achieved in the cycloaddition. The absolute stereochemistries of the major enantiomers of 5l, 5m, and 6d were determined unambiguously by X-ray crystallographic analysis: trans-(2R,4R)-5l, cis-(2S,4R)-5l, 4R-5m, trans-(2S,4S)-6d, and cis-(2R,4S)-6d were major enantiomers. Based upon the absolute stereochemistries of the major enantiomers, the mechanism of catalytic asymmetric induction in the cycloaddition reaction is discussed.

Diels-Alder cycloadditions of 2(1H)-quinolones having an electron-withdrawing group at the 3-position acting as dienophiles with dienes.

Diels-Alder cycloadditions of 2(1H)-quinolones having an electron-withdrawing group at the 3-position with alkyl- and silyloxy-1,3-butadienes (2a,b) were carried out to give phenanthridones richly functionalized regio- or stereoselectively under conditions of atmospheric and high pressure. Furthermore, regioselectivity and chemoselectivity of 3-substituted 2(1H)-quinolones to 2a, b were examined using MO calculation.

A stable bicyclic compound with two Si=Si double bonds.

In contrast to carbon, silicon does not readily form double bonds, and compounds containing silicon-silicon double bonds can usually be stabilized only by protection with bulky substituents. We have isolated a silicon analog of spiropentadiene 1, a carbon double-ring compound that has not been isolated to date. In the crystal structure of tetrakis[tri(t-butyldimethylsilyl)silyl]spiropentasiladiene 2, a substantial deviation from the perpendicular arrangement of the two rings is observed, and the silicon-silicon double bonds are shown to be distorted. Spectroscopic data indicate pronounced interaction between two remote silicon-silicon double bonds in the molecule. Silicon-silicon bonds may be more accessible to synthesis than previously assumed.

Structure of methyl adenophorate and triphyllol, triterpenoids of Adenophora triphylla var. japonica roots.

From the crude drug "shajin", the roots of Adenophora triphylla var. japonica, two novel triterpenoids, methyl adenophorate and triphyllol, have been isolated and these structures have been determined as those represented by formula I and II, respectively, on the basis of chemical and physical evidence.