Synthesis and Application of Highly Coordinated Nitrogen-Ligands

高度配位氮配体的合成及应用

• 批准号: 08455425
• 负责人: NISHIYAMA Hisao
• 金额: $ 4.54万
• 依托单位: Toyohashi University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455425/
• 关键词: nitrogen ligand; optically active; asymmetric induction; stereo control; catalysis; 不斉合成; ルテニウム; ミクロプロバン化; エポキシ化; オキサゾリン; ルテニウム錯体; 立体選択性; 酸化反応; ピリジン系配位子; 不斉エポキシ化; ジアセトキシヨードベンゼン; オレフィン; 金属錯体

1) Highly coordinated nitrogen-ligands were synthesized to be applied to asymmetric catalytic cylcopropanation of olefins with ruthenium catalysis. The intermediate carbene complexes were determined by NMR and X-ray analysis, and its geometry and moleculer orbitals were considered.2) Single chiral version of nitrogen-ligand were discovered and applied to asymmetric cyclopropanation to give high enantioselectivity.3) Chiral oxazoline ligand designed in this research exhibited high efficiency in asymmetric cylcopropanation over 80% ees.4) New nitrogen-benzene ligands were developed for asymmetric catalysis. One of them exhibited high efficiency in asymmetric allylation of aldehydes, and the catalyst proved to be recovered for reuse.

1)合成了高配位氮配体，并将其应用于Ru催化的烯烃不对称环丙烷化反应。通过核磁共振和X-射线分析确定了中间体卡宾化合物的结构，并考虑了其几何构型和分子轨道。2)发现了单手性氮配体，并将其应用于不对称环丙化反应中，获得了较高的对映体选择性。3)本研究设计的手性恶唑啉配体在不对称环丙化反应中表现出80%以上的高效率。4)合成了用于不对称催化的新型氮苯配体。其中一种催化剂对醛的不对称烯丙化反应表现出很高的效率，催化剂被回收重复使用。

项目成果

Motoyama.Y. ; Murata, K. ; Kurihara, O. ; Nitoh, T. ; Aoki, K. ; Nishiyama, H.: "Enantiofacially selective olefin coordination of alpha, beta-unsaturated carbonyl compounds to chiral bis (oxazolinyl) pyridineruthenium fragments" Organometallics. 17. 1251

本山.Y.

Y.Motoyama, H.Nishiyama: "Chiral Bis(Oxazolinyl)phenylrodium(III)Complexes as Lounis Acid Catalysts" J.Chem.Soc.,Chem Comm.(in press). (1999)

Y.Motoyama，H.Nishiyama：“手性双（恶唑啉基）苯基铑（III）配合物作为 Lounis Acid 催化剂”J.Chem.Soc.，Chem Comm.（印刷中）。

Nishiyama, H. ; Shimada, T. ; Itoh, H. ; Sugiyama, H. ; Motoyama, Y: "Novel rethenium-pyridinecarboxylate complexes of terpyridine and chiral bis (oxazolinyl) pyridine : a new catalytic system for alkene epoxidation with [bis (acetoxyl) iodo] benzene as a

西山，H.；

Doyle, M.P ; Peterson, C.S. ; Zhou, Q.-L. ; Nishiyama.H.: "Comparative evaluation of enantioscontrol for intramolecular cyclopropanation of diazoacetates with chiral Cu (I), Rh (II) and Ru (II) catalysts" J.Chem.Soc., Chem.Commun. 211 (1997)

多伊尔，议员；

H.Nishiyama, et al: "Single Chiral bis(oxazolinyl)pyridine Efficiency in Asymmetric catalytic cyclopropanation" Tetrahedron : Asymmetry. 9. 2865-2869 (1998)

H.Nishiyama 等人：“不对称催化环丙烷化中的单手性双（恶唑啉基）吡啶效率”四面体：不对称性。