Reactive Organometallics of Non-transition Metals

非过渡金属反应性有机金属化合物

• 批准号: 05236102
• 负责人: OKAZAKI Renji
• 金额: $ 44.03万
• 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 on Priority Areas
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05236102/
• 关键词: Organosilicon compounds; Organogermanium compounds; Organotin compounds; Organoantimony compounds; Organobismuth compoun; Assymetric alkylation; Kinetic stabilization; X-ray crystallograhy; ゲルマンテロン; 不斉触媒反応; 高配位スズ化合物; ヒドリドンリカート; 高配位化合物; オルトキノジ

The organic compounds of main group elements belonging to groups 12-15 were studied. (1) Heavier element analogs of ketones containing a Ge=X bond (X=S,Se, Te) were synthesized taking advantage of kinetic stabilization of a 2,4,6-tris [bis (trimethylsilyl) methyl] phenyl group and their structures and reactivities were investigated (Okazaki). (2) Asymmetric alkylation of aldehydes using alkylzinc compounds of an optically active amino alcohol, (-) - (2S) -3-exo- (dimethylamino) -isoborneol, was studied. The mechanism of the reaction was elucidated by examing the thermodynamic stability of the dimer of the zinc reagent, and the nonlinearity effect of the equilibrium constants (Noyori). (3) A new type of tin hydrides Bu_2SnXH (X=F,Cl, Br, I) was developed and the effect of halogen and/or complexation on the selectivity and reduction ability was studied (Baba). (4) High coordinate silicon compounds were synthesized as synthons of allyl anion, hydride ion, and vinyl anion. For example, allylsilanes underwent either allylation or [2+2] cycloaddition depending on the receptors (Hosomi). (5) Nitrogen containing bicyclic germanium and tin compounds were synthesized in order to study the ability of group 14 element compounds as a carbon nucleophile. The Pd catalyzed coupling reaction with halogenated compounds was developed and applied to the synthesis of natural products (Migita). (6) Five coordinate organoantimony and bismuth compound were prepared and their structures were established by X-ray crystallographic analysis. The pseudorotation of these compounds were accelerated by a nucleophile such as a fluoride ion (Yamamoto).

研究了12-15族主族元素的有机化合物。(1)利用2，4，6-三[双(三甲基硅基)甲基]苯基的动力学稳定性，合成了含Ge=X键的酮类重元素化合物(X=S，Se，Te)，并研究了它们的结构和反应活性(Okazaki)。(2)研究了旋光性氨基醇烷基锌化合物(-)-(2S)-3-外-(二甲氨基)-异龙脑催化醛的不对称烷基化反应。通过考察锌试剂二聚体的热力学稳定性和平衡常数的非线性效应(Noyori)，阐明了反应机理。(3)合成了一种新型锡氢化物Bu_2SnXH(X=F，Cl，Br，I)，研究了卤素和/或络合对其选择性和还原能力的影响(BABA)。(4)以烯丙基阴离子、氢化氢离子和乙烯基阴离子为原料合成了高配位硅化合物。例如，烯丙基硅烷根据受体的不同进行了烯丙化或[2+2]环加成反应(Hosomi)。(5)合成了含氮双环锗和锡化合物，研究了14族元素化合物作为碳亲核试剂的能力。发展了钯与卤代化合物的偶联反应，并将其应用于天然产物Migita的合成。(6)合成了五种有机锑铋配位化合物，并通过X-射线单晶分析确定了它们的结构。这些化合物的假旋转被一种亲核试剂加速，如氟离子(山本)。

项目成果

R.Okazaki: "The First Rotational Isomers of Stable Selenoaldehydes and Their 1-Tungsten Complex" Angew.Chem.,Int.Ed.Engl.35. 660-662 (1996)

R.Okazaki：“稳定硒醛及其 1-钨配合物的第一个旋转异构体”Angew.Chem.，Int.Ed.Engl.35。

T.Matsumoto: "Syntnesis and Structure of the First Stable Germaneselone" Angew. Chem., Int. Ed. Engl.33. 2316-2317 (1993)

T.Matsumoto：“第一个稳定的日耳曼塞隆的合成和结构”Angew。

H.Oda: "Palladium-catalyzed Ternary Coupling Reaction of Aryl Halide, Phenyltiributyltin and Norbornadiene" Chem. Lett.1443-1444 (1994)

H.Oda：“芳基卤化物、苯基三丁基锡和降冰片二烯的钯催化三元偶联反应”Chem。

N.Tokitoh: "The First Stable 1,2-Thiastannete and 1,2-Selenastannete:Their Syntheses and Crystal Structures" J.Chem.Soc.,Chem.Commun.407-409 (1993)

N.Tokitoh：“第一个稳定的 1,2-Thiastannete 和 1,2-Selenastannete：它们的合成和晶体结构”J.Chem.Soc.,Chem.Commun.407-409 (1993)

Y.Yamamoto: "Synthesis and Structure of Six-Coordinated Organobismuth Compounds with Bidentate Ligands(12-Bi-6)" Organometallics. 12. 3297-3303 (1993)

Y.Yamamoto：“具有双齿配体（12-Bi-6）的六配位有机铋化合物的合成和结构”有机金属化合物。