Grant-in-Aid for Overseas Scientific Survey.
|Research Institution||Ehime University|
TODA Fumio Ehime University, Professor, 工学部, 教授 (50036232)
BOURNE Susan University of Cape Town, Assistant Professor, 化学科, 主任研究員
CAIRA Mino R ケープタウン大学, 化学科, 助教授
NASSIMBENI L ケープタウン大学, 化学科, 教授
ELGUERO Jose CSIC,Professor, 教授
宮本 久一 愛媛大学, 工学部, 助手 (30229893)
田中 耕一 愛媛大学, 工学部, 助教授 (10116949)
NASSIMBENI Luigi r. University of Cape Town, Professor
TANAKA Koichi Ehime University, Associate Professor
MIYAMOTO Hisakazu Ehime University, Assistant Professor
CAIRA Mino University of Cape Town, Associate Professor
|Project Fiscal Year
1993 – 1994
Completed(Fiscal Year 1994)
|Budget Amount *help
¥7,000,000 (Direct Cost : ¥7,000,000)
Fiscal Year 1994 : ¥3,500,000 (Direct Cost : ¥3,500,000)
Fiscal Year 1993 : ¥3,500,000 (Direct Cost : ¥3,500,000)
|Keywords||molecular assembly / inclusion complex / host-guest / solid state reaction / enantioselective reaction / X-ray analysis / 包接結晶 / ホストーゲスト / 分子認識 / 不斉認識 / X線解析 / 熱力学的測定 / アンモニウム塩 / 光学分割 / 分子集合体 / 選択的反応 / 分子配列制御 / 熱分析 / 平衡凍結|
In crystalline molecular assemblysuch as crystalline host-guest inclusion complex, molecules are arraged regularly and then chemical reactions would proceed selectively. When chiral host is used, prochiral guest molecules are arranged in a chiral form in the inclusion complex. Photochemical or thermochemical reactions of the prochiral guest in the inclusion complex would give chiral reaction product. On the other hand, when the inclusion complexation between host and a mixture of isomers occurs selectively, separation of isomers can be carried out by the inclusion complexation. When a chiral host is used, separation of enantiomers can be accomplished. Furthermore, in these crystalline molcular assembly, molecular isomerization such as tautomerism is restricted or frozen, and then one tautomer can be isolated in pure form. In these topics, our collaboration works have been done.
1) Achiral oxoamides formed inclusion complex with chiral host compound derived from tartaric acid. Photoirradiation of the inclusion crystal in the solid state gave optically active beta-lactam derivative. In most cases, enantioselectivity of the solid state reaction is very high. Arrangement of the prochiral oxoamide molecules in a chiral form has been studied by X-ray crystal structure analysis. Some other prochiral compounds which have diene grooups are also arrranged in a chiral form in an inclusion crystal with chiral host, and photoirradiation of the crystal gave optically active 2+2 photocyclization product.
2) Reaction of an inclusion complex of 2-cyclohexenone and a chiral host derived from tartaric acid with dienophile in the solid state gave optically active Michael addition product. In the solid state reaction, dienophile recognizes the upside and downside of the molecular plane of 2-cyclohexenone.
3) Some ammonium salt host compounds included phenole derivatives X-ray crystal structures were studied.