| Research Abstract |
We have investigated organic synthesis utilizing the characteristic properties of such hetero atoms as sulfur, nitrogen, and fluorine atoms to obtain the following fruitful results.
i) Efficient 1,2-asymmetric induction in a radical addition : 1-Hydroxyalkyl radicals were found to add to gamma-hydroxy alpha-thio alpha, beta-unsaturated sulfones (or carboxylic esters) were revealed with extremely high efficiency. This is attributable to the conformational fixation around the beta, gamma-bond and the radical stabilization by a synergistic (captodative) effect of thio and sulfonyl (alkoxycarbonyl) groups.
ii) Novel construction of a benzene ring : 1-methylthio (or chloro) -3- (p-tolylsulfonyl) -1,3,5-alkatrienes were found to thermally or photochemically give rise to benzene derivatives. We also found a novel construction of a benzene ring from a 1,3-alkadiene-5-yne.
iii) Functional materials containing nitrogen and sulfur atoms : 1-Aryl-2,5di (2-thienyl) pyrroles, a new type of pi-electron
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systems, were shown to make it possible to develop efficient third-order nonlinear optics and EL-devices.
iv) New synthesis of perfluoroethylidene-containing compounds : We found that a perfluoropropene-diethylamine adduct (PPDA) reacts with various allyl alcohols to form alpha-fluoro-alpha-trifluoromethyl-gamma-lactones and alpha-fluoro-alpha-trifluoromethyl-gamma, delta-unsaturated amides which are useful synthetic intermediates of many kinds of perfluoroethylidene-containing compounds.
v) Self-assembly of macromolecules using reversible pyridine-palladium coordination bonds : Di-or tri (4-pyridyl) -containing ligands were found to react (en) Pd (NO3) 2 (en=ethylene diamine) in a selfassmbly manner to produce macromolecules such catenanes and three-dimensional cage-type compounds.
vi) Molecular recognition in dipeptide crystals : (R) -Arylglycyl- (R) -phenylglycines (aryl=phenyl or 1-naphthyl) form inclusion crystals with various guest molecules. In the crystal, dipeptide molecules construct sheet structures and the guest molecules are accommodated between the sheets by means of hydrogen bonding, CH-pi interaction, and phenyl-phenyl edge-to-face interaction. Less
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