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Development of Novel Transformation on Polynuclear Transition Metal Complexes

多核过渡金属配合物的新型转化研究进展

基本信息

批准号：
18350048
负责人：
NISHIBAYASHI Yoshiaki
金额：
$ 10.32万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

We have developed novel transformations only promoted by polynuclear transition metal complexes such as heteroatom-bridged diruthenium complexes. We have newly found the following three topics. (1) We have found enantioselective propargylation of aromatic compounds such as N,N-dimethylanilines, 2-methylfuran, and N-substituted indoles with propargylic alcohols catalyzed by thiolated-bridged diruthenium complexes bearing optically active thiolate ligands to give the corresponding propargylated aromatic compounds in good to high yields with a high enantioselectivity (up to 94% ee). (2) We have found novel reactions between propargylic alcohols and acetone catalyzed by dicationic chalcogenolated-bridged diruthenium complexes to give the corresponding hexadienones in moderate to good yields, in sharp contrast to the formation of γ-ketoalkynes when neutral or monocationic diruthenium complexes are employed as catalysts. (3) We have newly prepared phosphido-bridged diruthenium complexes and investigated their catalytic activity toward reactions of propargylic alcohols with aromatic compounds to give the corresponding α,β-unsaturated ketones in moderate yields. In addition, we have developed novel some reactions catalyzed by thiolate-bridged diruthenium complexes such as vinylic substitution reactions with nucleophiles via butatrienylidene complexes as key intermediates.

我们已经开发了新的转换，只有促进多核过渡金属配合物，如杂原子桥连双钌配合物。我们新发现了以下三个主题。(1)我们已经发现了芳香族化合物，如N，N-二甲基苯胺，2-甲基呋喃，和N-取代吲哚与炔丙醇的不对称炔丙基化反应，硫醇化桥联双钌配合物具有光学活性硫醇配体催化，得到相应的炔丙基化芳香族化合物在良好的高收率和高对映体选择性（高达94%ee）。(2)我们发现了一种新颖的炔丙醇与丙酮的反应，在双阳离子硫族桥联双钌配合物的催化下，以中等至良好的产率得到相应的己二烯酮，与中性或单阳离子双钌配合物作为催化剂时形成的γ-酮基炔形成鲜明对比。(3)我们合成了磷桥联双钌配合物，并研究了它们对炔丙醇与芳香族化合物反应的催化活性，以中等产率合成了相应的α，β-不饱和酮。此外，我们还开发了一些新的硫醇桥联双钌配合物催化的反应，如通过丁三烯叉配合物作为关键中间体与亲核试剂的乙烯基取代反应。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Ruthenium-Catalyzed Reductive Coupling Reaction of Propargylic Alcohols via Hydroboration of Allenylidene Intermediates

钌催化丙炔醇通过烯叉中间体硼氢化反应的还原偶联反应

DOI：
发表时间：
2006
期刊：
Organometallics 25
影响因子：
0
作者：
Yukinori Sudo;Shigeru Arai;Atsushi Nishida;H.Usui;保田英洋;H.Usui;A.Tanaka;Y.Shimada et al.;Y.Nishibayashi et al.;G.Onodera et al.
通讯作者：
G.Onodera et al.

Ruthenium‐Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols