Organic Synthesis Utilizing the Characteristic Properties of Hetero Atoms

我们利用硫、氮、氟等杂原子的特性对有机合成进行了研究，取得了以下卓有成效的结果：i)在自由基加成中有效地1，2-不对称诱导：1-羟基烷基自由基被发现加到α-硫代-α-羟基中，β-不饱和磺酸(或羧酸酯)被发现具有极高的效率。这是由于硫代和磺基(烷氧基)基团的协同(捕捉)效应对β，γ键的构象固定和自由基的稳定。ii)苯环的新结构：1-甲硫基(或氯)-3-(对甲苯基磺酰基)-1，3，5-烷基三烯以热或光化学的方式产生苯衍生物。我们还发现了一种由含氮和硫原子的功能材料1-芳基-2，5二(2-噻吩基)吡咯-1-芳基-2，5二(2-噻吩基)吡咯构筑苯环的新方法，这是一种新型的pi-电子…IV)全氟乙叉化合物的新合成：我们发现全氟丙烯-二乙胺加合物(PPDA)与各种烯丙醇反应生成alpha-fluoro-alpha-trifluoromethyl-gamma-lactones和α-氟-α-三氟甲基-伽马，V)利用可逆吡啶-钯配位键的大分子自组装：二或三(4-吡啶)配体被发现以自组装的方式与(EN)Pd(NO3)2(EN=乙二胺)反应生成大分子，如Catenane和三维笼型化合物。vi)二肽晶体中的分子识别：(R)-芳基甘氨基-(R)-苯基甘氨酸(芳基=苯基或1-萘基)与各种客体分子形成包合物。在晶体中，二肽分子构成片状结构，客体分子通过氢键、CH-pi相互作用和苯基-苯基边对面相互作用在片状结构之间进行调节。较少

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 … More 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