Grant-in-Aid for Scientific Research (A)
|Allocation Type||Single-year Grants|
|Research Institution||Kochi University|
KOTSUKI Hiyoshizo Kochi University, Faculty of Science Department of Materials Science, Professor, 理学部, 教授 (80093954)
YANAGISAWA Kazumichi Kochi University, Faculty of Science Lab of Hydrothermal Chemistry, Professor, 理学部, 教授 (90145110)
ICHIKAWA Yoshiyasu Kochi University, Faculty of Science Department of Materials Science, Professor, 理学部, 教授 (60193439)
GAMOH Keiji Kochi University, Faculty of Education Department of Chemistry, Professor, 教育学部, 教授 (90204817)
|Project Period (FY)
2002 – 2004
Completed(Fiscal Year 2004)
|Budget Amount *help
¥56,160,000 (Direct Cost : ¥43,200,000、Indirect Cost : ¥12,960,000)
Fiscal Year 2004 : ¥8,580,000 (Direct Cost : ¥6,600,000、Indirect Cost : ¥1,980,000)
Fiscal Year 2003 : ¥14,430,000 (Direct Cost : ¥11,100,000、Indirect Cost : ¥3,330,000)
Fiscal Year 2002 : ¥33,150,000 (Direct Cost : ¥25,500,000、Indirect Cost : ¥7,650,000)
|Keywords||High Pressure Reactions / Solvent-Free Reactions / Uncatalyzed Reactions / Hydrothermal Reactions / Asymmetric Organocatalysis / Condensation Reactions / Natural Product Synthesis / Organic Materials Synthesis / pincer-Diels-Alder反応 / 無触媒的アセタール化反応 / 無触媒的縮合反応 / 不斉アルドール反応 / 生理活性天然物合成 / 有機不斉塩基触媒 / 不斉Michael付加反応 / 水熱反応 / Diels-Alder反応 / 脱水縮合反応 / 芳香環アルキル化 / D化反応 / 異性化反応 / 還元的二量化 / 水中反応|
1.Diels-Alder Reaction of Less Reactive Dienes under High-Pressure/Solvent Free Conditions :
Dramatic effects of high-pressure/solvent-free conditions were recognized for the Diels Alder reaction of thiophene. Under the very similar conditions, domino- and pincer-Diels-Alder reactions of furan were performed. All of these adducts were not easily prepared by other means. From the viewpoint of atom economy these provide a unique method in organic synthesis.
2.Uncatalyzed Functional Group Transformations under High-Pressure/Solvent-Free Conditions :
Several important methods for the functional group transformations were developed under high-pressure/solvent-free conditions in the absence of any catalysts. For example, the synthesis of pyridine-thiourea conjugates via condensation between isothiocyanates and aminopyridines, acetalization of ketones, synthesis of substituted ureas via condensation of trichloroethylcarbamates with amines, Strecker reaction using aromatic ketones/aromatic amines
/ trirnethylsilyl cyanide.
3.Novel Synthesis of Nitrogen Heterocycles via Condensation of Ketones under Hydrothermal Conditions :
Cyclocondensation of cyclic ketones in hot aqueous ammonium chloride gave fully substituted pyridine derivatives in good yields. On the other hand, treatment of o-phenylaniline hydrochloride salts with cyclic ketones in hot water produced phenanthridine derivatives in good yields. These are all typical examples of novel use of hydrothermal chemistry in organic synthesis and contribute to the development of environmentally friendly organic synthesis.
4.Aromatic H-D Exchange Reactions under Hydrothermal Conditions in D20 :
The efficient method for H-D exchange reactions of aromatic amines was developed by conducting the reactions in D2O under hydrothermal conditions.
5.Development of Novel Asymmetric Organocatalysts :
Novel synthesis of chiral pyrrolidine-pyridine conjugate base catalysts was performed, and these catalysts were applied for the asymmetric Michael addition reaction of ketones with nitroolefins. The results were excellent in view of catalytic activity, diastereoselectivity, and enantioselectivity.
6.Organocatalytic Asymmetric Synthesis of Natural Products :
Novel straight chain aliphatic aldehyde synthons were developed for the use in L-proline catalyzed asymmetric aldol reactions. The utility of this method was exemplified by the short synthesis of oviposition attractant pheromone, sphyngosines, boronolide in optically pure forms.
7.Miscellaneous Organic Functional Group Transformations:
Cis/traps isomerization of 4-substituted cylohexylbenzene derivatives, liquid crystalline materials, under the catalysis of TfOH. Less