Structure-Reactivity Relationship for Organic Small Molecule-Metal Complexes

有机小分子-金属配合物的结构-反应性关系

• 批准号: 05453138
• 负责人: KUROSAWA Hideo
• 金额: $ 4.42万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 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-05453138/
• 关键词: pi-Allyl complex; Trimethylenemethane complex; Oxatrimethylenemethane complex; パラジウム錯体

The objective of this research project is to establish structure-reactivity relationship in organic small molecule-transition metal complexes, and to apply such relation to selective organic synthesis.1) Stereochemical control of pi-allylic complexes. Requirements for 1-substituted allyl ligands to assume unusual anti-sterochemistry have been established by means of their coordination to dimetallic moieties. Enantioselective coordination of these ligands to Pd was realized by the use of bis(oxazoline) ligand.2) Structure and reactivity of trimethylenemethane ligand and its analogs. Trimethylenemethane-palladium intermediate has been generated by means of destannylation of 2-stannylmethylallypalladium complexes, which reacted with aldehydes in a formal [2+3] cyclization manner. Analogous oxotrimethylenemethanepalladium complexes have been prepared, and their structure revealed by X-ray analysis. These complexes reacted with norbornene via [1+2] cycloadditon.3) Synthesis and structure of mu-Allyl, mu-Propargyl and mu-butadiene dimetallic complexes. A general method for obtaining mu-allyl, mu-propargyl and mu-butadiene Pd-Pd complexes has been developed, which consists of reacting organopalladium(II) complexes with Pd(0) complexes. X-ray structure analysis revealed a characteristic Pd_2X framework which is bridged by organic small ligands.

本研究项目的目的是建立有机小分子-过渡金属配合物的结构-反应性关系，并将这种关系应用于选择性有机合成。1）π-烯丙基配合物的立体化学控制。 1-取代的烯丙基配体呈现不寻常的反立体化学的要求已经通过它们与二金属部分的配位而确定。利用双(恶唑啉)配体实现了这些配体与Pd的对映选择性配位。2)三亚甲基甲烷配体及其类似物的结构和反应活性。三亚甲基甲烷-钯中间体是通过2-甲锡烷基甲基烯丙基钯络合物与醛以正式[2+3]环化方式反应生成的。类似的氧代三亚甲基甲烷钯配合物已被制备出来，并通过 X 射线分析揭示了它们的结构。这些配合物与降冰片烯通过[1+2]环加成反应。3）mu-烯丙基、mu-丙炔和mu-丁二烯二金属配合物的合成和结构。开发了一种获得μ-烯丙基、μ-炔丙基和μ-丁二烯Pd-Pd配合物的通用方法，该方法包括使有机钯(II)配合物与Pd(0)配合物反应。 X射线结构分析揭示了由有机小配体桥接的特征性Pd_2X骨架。

项目成果

Kenzo Ohkita, Hideo Kurosawa, Takeya Hasegawa, Toshikazu Hirao, and Isao Ikeda: "Highly Stereoselective Coordination of Monosubstituted eta^3-Allyl Groups to ChiralBis(oxazoline) palladium Cation." Organometallics. 12. 3211-3215 (1993)

Kenzo Ohkita、Hideo Kurosawa、Takeya Hasekawa、Toshikazu Hirao 和 Isao Ikeda：“单取代 eta^3-烯丙基与手性双（恶唑啉）钯阳离子的高度立体选择性配位。”

Hideo Kurosawa,他4名: "Regiochemical control in Reductive Elimination of (n^3-Crotyl)Caryl-palladium(II)Complexes" J.Chem.Soc.Chem.Comm. 1099-1100 (1994)

Hideo Kurosawa 和其他 4 人：“(n^3-Crotyl)Caryl-palladium(II) Complexes 还原消除中的区域化学控制”J.Chem.Soc.Chem.Comm 1099-1100 (1994)

黒沢英夫,他4名: "Highly Stereoselective Coordination of Monosubstituted η^3-Allyl Group to Chiral Bis(oxazoline)palladium Cation" Organometallics. 12. 3211-3215 (1993)

Hideo Kurosawa 和其他 4 人：“单取代 η^3-烯丙基与手性双(恶唑啉)钯阳离子的高度立体选择性配位”有机金属学 12. 3211-3215 (1993)

Hideo Kurosawa, Kenjin Shiba, Kazuyoshi Hirako, Kiyomi Kakiuchi, and Isao Ikeda: "Regiochemical Control in Reductive Elimination of (eta^3-Crotyl)(aryl)palladium(II) Complexes." J.Chem.Soc., Chem.Commun.1099-1100 (1994)

Hideo Kurosawa、Kenjin Shiba、Kazuyoshi Hirako、Kiyomi Kakiuchi 和 Isao Ikeda：“(eta^3-Crotyl)(aryl)palladium(II) Complexes 还原消除中的区域化学控制。”

Akihiro Ohsuka,Hideo Kurosawa,他2名: "Structural study of oxydimethylenemettene-palladium and-platinum complexes" Organometallics. (印刷中). (1995)

Akihiro Ohsuka、Hideo Kurosawa 和其他 2 人：“氧二亚甲基-钯和铂复合物的结构研究”有机金属学（1995 年）。