Development of New Photo-, Electric-, and Molecular-Devised Materials Using High Pressure Technology

（a） Michael Addition Reactions of？-Ketoesters： Michael Addition reactions of？-ketoesters with a variety of？，？-unsaturated carbonyl compounds using Yb（OTf）イイD23イエD2 / SiOイD22イエD2 or TfOH under solvent-free conditions have been established。在添加剂中，同源-迈克尔添加剂反应使用激活的环丙烷衍生物在很高的压力下实现。（b）使用新型氮杂环进行非对称催化：已开发的催化剂对催化剂有效烷基化的使用中的七支吡啶和二硫醚衍生的配体。（c）五氮唑啉化合物的合成：一种五氮唑啉衍生物已经准备好了在良好的年份中使用氰化物和氮激活的O氟代苯并醛的条件。（d） Supported Reactions on Silica Gel ： Solvent-free organic reactions on silica gel supports have been·ped： transformation of epoxides to halohydrins using LiX /SiOD22·D2 and chemoselective deprotection of N-Boc carboxamides using Yb（OTf）···D23···D2/·D2·D2。（e）天然产品合成：AI-77-B的一种有效总合成，一种天然保护性物质从芽孢杆菌AI-77的培养中分离出来，在高覆盖率下表现良好。（f）使用高压技术进行分子模板成形：在高压条件下形成骨胶原血清albumin-silica凝胶的分子模板，并用于手性高效液相色谱法分析已被执行。（g） Functional Group Transfonnations ： Chemoselective reductive transformation of azides to N-Boc protected amines ， Sc（OTf）y D23 y D2-or TfOH-catalyzed Baeyer-Villiger oxidation and high-pressure-promoted LiClO）y D24 y D2-catalyzed epoxides reaction of epoxides with furans or thiophenes。

(a) Michael Addition Reactions of β-Ketoesters : Michael addition reactions of β-ketoesters with a variety of α, β-unsaturated carbonyl compounds using Yb(OTf)ィイD23ィエD2 / SiOィイD22ィエD2 or TfOH under solvent-free conditions have been established. In addition, homo-Michael addition reaction using activated cyclopropane derivatives has been achieved at high pressure.(b) Asymmetric Catalysis Using Novel Nitrogen Heterocycles : Several chiral dipyridine and dithiophene derived ligands for the use in the catalytic enantioselective alkylation have been developed.(c) Synthesis of Quinazoline Compounds : A variety of quinazoline derivatives have been prepared by condensation of cyano- and nitro-activated o-fluorobenzaldehydes with amidines in good yields.(d) Supported Reactions on Silica Gel : Solvent-free organic reactions on silica gel supports have been developed: transformation of epoxides to halohydrins using LiX / SiOィイD22ィエD2 and chemoselective deprotection of N-Boc carboxamides using Yb(OTf)ィイD23ィエD2/ SiOィイD22ィエD2.(e) Natural Product Synthesis : An enantioselective total synthesis of AI-77-B, a gastroprotective substance isolated from a culture broth of Bacillus pumilus AI-77, has been performed in high overall yield.(f) Molecular Template Formation Using High Pressure Technique : Molecular template formation of bovine serum albumin-silica gels under high pressure conditions and its use for chiral HPLC analysis have been performed.(g) Functional Group Transfonnations : Chemoselective reductive transformation of azides to N-Boc protected amines , Sc(OTf)ィイD23ィエD2- or TfOH-catalyzed Baeyer-Villiger oxidation and high-pressure-promoted LiClO)ィイD24ィエD2 -catalyzed reaction of epoxides with furans or thiophenes .