Development of Highly Efficient Organometallic Catalysis for Short-step Assembly of Complex Moleculer Structures

开发用于复杂分子结构短步组装的高效有机金属催化

• 批准号: 12450360
• 负责人: ITOH Kenji
• 金额: $ 10.62万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450360/
• 关键词: Homogeneous Catalysis; Ruthenium; Palladium; Rhodium; Iridium; Multicomponent Coupling; Organometallic Complex; 触媒的炭素結合形成; 触媒的付加環化; メタラサイクル中間体; ルテニウム錯体触媒; ロジウム錯体触媒; イリジウム錯体触媒; 複素環合成; パラジウム錯体触媒; ピリジン骨格合成; メタラシクペンタジエン

1. In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=0 double bonds to selectively afford dienones via electrocyclic ring opening of the expected α-pyrans.2. The Pd(0)-catalyzed cyclization of electron-deficient diynes and triynes efficiently gave polycyclic aromatic coupounds. Their reaction mechanism was elucidated by means of the characterization of relevant intermediate complexes and density functional calculations of intermediate models.3. A rhodium-catalyzed method for the synthesis of β-amino esters was accomplished in a one-pot procedure from aldimine, α,β-unsaturated ester and hydosilane.4. Propargylic-type acetates react readily with enoxysilanes in the presence of a catalytic amount of a cationic iridium complex to give β-alkynyl ketones in high to excellent yields. Substitution at propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.

1.在催化量的Cp*Ru（cod）Cl存在下，具有多种官能团的不对称1，6-二炔与缺电子三羰基化合物在酮C=0双键处发生反应，通过电环开环反应选择性地生成二烯酮.在Pd（0）催化下，缺电子二炔和三炔的环化反应可有效地得到多环芳香化合物。通过对相关中间体配合物的表征和中间体模型的密度泛函计算，阐明了它们的反应机理.以醛亚胺、α，β-不饱和酯和硅烷为原料，铑催化一锅法合成了β-氨基酯.炔丙基型乙酸酯在催化量的阳离子铱络合物的存在下容易地与烯氧基硅烷反应，以高产率至优异的产率得到β-炔基酮。在大多数类型的炔丙基酯中，炔丙基碳上的取代是排他的或选择性的。或者，丙二烯基产物的形成在酯的反应中占主导地位，所述酯在炔丙基碳上具有两个苯基。