DEVELOPMENT OF NEW ASYMMETRIC REACTIONS BASED ON CONFORMATIONALY FIXED CYCLOALKANE-POLYOLS.

基于构象固定环烷烃多元醇的新型不对称反应的开发。

• 批准号: 05671755
• 负责人: SUEMUNE Hiroshi
• 金额: $ 1.09万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05671755/
• 关键词: Asymmetric synthesis; Asymmetric reaction; Configuration; Chiral cyclic diol; Chiral enol ether; Chelation

Based on our previous study for preparation of enantiomerically pure cycloalkane-1,2-diols by using enzymatic procedure, several asymmetric reactions have been developed in this research project.1)A new method for asymmetric construction of a quatemary carbon and its application to the synthesis of spiro-cyclic compound have been developed by using cycloalkane-1,2-diols as a chiral auxiliary.2)New types of asymmetric reactions have been developed by using "chiral enol ether" as a key intermediate : Two kinds of asymmetric Michael reaciton ; Asymmetric oxidation of beta-keto esters ; Chiral induction to meso-cyclic 1,2-diol.3)Asymmetric spiro-cyclization has been developed by using chiral cycloalkane-1,2-diol as a chiral sorce.

本课题在前人研究的基础上，发展了几种不对称反应：1）以环烷烃-1，2-二醇为原料，建立了一种不对称合成季碳的新方法，并将其应用于螺环化合物的合成，2）以“手性烯醇醚”为关键中间体，发展了几种新型的不对称反应：两种不对称Michael反应：β-酮酯的不对称氧化反应; 3）以手性环烷烃-1，2-二醇为手性源，开展了不对称螺环化反应。

项目成果

H.Suemune: "Highly Enantio-and Diastereoselective Synthesis of C_2-symmetric Cyclohexane-1,2,4,5-tetrol" Tetrahedron:Asymmetry. 6. 55-58 (1995)

H.Suemune：“C_2-对称环己烷-1,2,4,5-四醇的高度对映和非对映选择性合成”四面体：不对称。

Hiroshi Suemune: "Asymmetric Induction to meso-Cyclohexane-1,2-diol Based on Diastereoselective Elimination" Tetrahedron Asymmetry. 4. 1767-1770 (1993)

Hiroshi Suemune：“基于非对映选择性消除的内消旋环己烷-1,2-二醇的不对称诱导”四面体不对称性。

Hiroshi Suemune: "Activation of Carbonyl Function by1,2-Diol;Novel Asymmentric Spirocyclization Based on Acid-Catalyzed Conjugate Addition" J.Chem.Soc.,Chem.Commun.1858-1859 (1993)

Hiroshi Suemune：“1,2-二醇活化羰基功能；基于酸催化共轭加成的新型不对称螺环化”J.Chem.Soc.，Chem.Commun.1858-1859 (1993)

H.Suemune: "Activation of Carbonyl Function by 1,2-Diol;Novel Asymmetric Spirocylization Based on Acid-Catalyzed Conjugate Addition." J.Chem.Soc.,Chem.Commun.1858-1859 (1993)

H.Suemune：“1,2-二醇活化羰基功能；基于酸催化共轭加成的新型不对称螺环化。”

S.Nagumo: "Novel Ring Cleavage Based on Intermolecular Aldol Condensation." Tetrahedron. 49. 10501-10510 (1993)

S.Nagumo：“基于分子间羟醛缩合的新型环裂解。”