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.

该研究项目的目的是在有机小分子转换金属复合物中建立结构反应关系，并与选择性有机合成的这种关系。1）对Pi-Allylic复合物的立体化学控制。通过1通过协调对二胺的部分建立了对1个取代的Allyl配体的要求。这些配体对PD的对映选择性协调是通过使用双甲基甲烷配体及其类似物的结构和反应性来实现的。2）结构和反应性。三甲基甲烷 - 甲基 - 甲基 - 中间体是通过对2烷基甲基 - 甲基丙二酰络合物的杀伤性产生的，该甲基化合物以形式[2+3]环化方式与醛反应。已经制备了类似的氧甲甲基甲甲基苯甲酰甲基丙二酰辅基复合物，并通过X射线分析揭示其结构。这些复合物通过[1+2] cycloadditon与诺本烯反应。3）Mu-Alyl，Mu propargyl和Mu-butadiene二缩复合物的合成和结构。已经开发了一种获得Mu-酰基，MU-丙烷和Mu-butadiene PD-PD复合物的一般方法，该方法包括与PD（0）复合物的反应有机甲帕（II）复合物。 X射线结构分析揭示了一个特征性的PD_2X框架，该框架由有机小配体桥接。

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。”

Saisuke Watanabe,Hideo Kurosawa,他2名: "Synthesis of n^3-2-stannuylmethylallylpalladium complexes and their destannylation leading to trimethylene methane-palladium species" J.Organomet.Chem.481. 19-25 (1994)

Saisuke Watanabe、Hideo Kurosawa 和另外 2 人：“n^3-2-甲锡基甲基烯丙基钯复合物​​的合成及其脱锡烷基化导致三亚甲基甲烷-钯物质”J.Organomet.Chem.481 (1994)。