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Development of Catalytic Asymmetric Reactions with High Efficiency

高效催化不对称反应的发展

基本信息

批准号：
14078216
负责人：
HAYASHI Tamio
金额：
$ 16.38万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

One of the most significant subjects for developing catalytic asymmetric reactions is the design and preparation of a chiral ligand which will fit in with a given reaction efficiently in catalytic activity and enantioselectivity. A number of chiral molecules containing phosphorus and/or nitrogen atoms have been prepared and used for transition metal-catalyzed asymmetric reactions, but they are not always useful as chiral ligands because of their low catalytic activity or enantioselectivity. In this research project, as conceptually new chiral ligands, we have introduced a series of chiral dienes which opened up a new dimension in the field of asymmetric catalysis. The chiral dienes are based on bicyclo [2.2.1] heptadiene (nbd^*), bicyclo [2.2.2] octadiene (bod^*), or bicyclo [3.3.1] nonadiene (bnd^*) skeleton. The chiral diene ligands were found to be very effective for rhodium-catalyzed asymmetric 1,4-addition of arylboron reagents to electron deficient olefins, 1,2-addition to N-sulfonylimines, and so on. The enantioselectivities observed with the chiral diene ligands are very high compared with those observed with other types of chiral ligands such as chiral bisphosphines. It is remarkable that the catalytic activity of the rhodium catalysts coordinated with the diene ligands is much higher than with conventional phosphorus ligands, which made it possible to realize the catalytic asymmetric reactions with a very small amount (<0.005 mol %) of the catalyst.

手性配体的设计和制备是发展催化不对称反应的重要课题之一，它能有效地配合特定的反应，具有催化活性和对映选择性。许多含磷和/或氮原子的手性分子已被制备并用于过渡金属催化的不对称反应，但它们并不总是有用的手性配体，因为它们的低催化活性或对映选择性。在本研究计划中，我们引入了一系列的手性二烯化合物作为新的手性配体，为不对称催化领域开辟了新的方向。手性二烯基于双环[2.2.1]庚二烯（nbd^*）、双环[2.2.2]辛二烯（bod^*）或双环[3.3.1]壬二烯（bnd^*）骨架。手性二烯配体在铑催化的芳基硼试剂对缺电子烯烃的不对称1，4-加成反应、对N-磺酰亚胺的不对称1，2-加成反应等反应中表现出很高的对映选择性.值得注意的是，与二烯配体配位的铑催化剂的催化活性比与常规磷配体配位的催化活性高得多，这使得可以用非常少量（<0.005mol%）的催化剂实现催化不对称反应。

项目成果

期刊论文数量（133）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Rhodium-catalyzed asymmetric synthesis of indanones: development of a new "axially chiral" bisphosphine ligand.

DOI：
10.1002/chin.200629083
发表时间：
2006-02
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
R. Shintani;Keiji Yashio;Tomoaki Nakamura;K. Okamoto;Toyoshi Shimada;Tamio Hayashi
通讯作者：
R. Shintani;Keiji Yashio;Tomoaki Nakamura;K. Okamoto;Toyoshi Shimada;Tamio Hayashi

A New Entry of Nucleophiles in Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions : Addition of Oranozinc Reagents for the Synthesis of 2-Aryl-4-Piperidones

铑催化不对称 1,4-加成反应中亲核试剂的新进入：添加 Oranozinc 试剂合成 2-芳基-4-哌啶酮

DOI：
发表时间：
2004
期刊：
J. Am. Chem. Soc. 126
影响因子：
0
作者：
Hidetaka Sonoda;Gentaro Watanabe;Katsuhiko Sato;Tomoya Takiwaki;Kenji Yasuoka;Toshikazu Ebisuzaki;佐川貴志;新谷亮
通讯作者：
新谷亮

Rhodium-catalyzed asymmetric hydroarylation of diphenylphosphinylallenes with arylboronic acids