Reactive Organometallics of Non-transition Metals

研究了12-15族主族元素的有机化合物。(1)利用2，4，6-三[双（三甲基甲硅烷基）甲基]苯基的动力学稳定化合成了含有Ge=X键（X=S、Se、Te）的酮的较重元素类似物，并研究了它们的结构和反应性（Okazaki）。(2)研究了光学活性氨基醇（-）-（2S）-3-外-（二甲氨基）-异冰片的烷基锌化合物与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)本文报道了一种新型的锡配合物Bu_2SnXH（X=F，Cl，Br，I），并研究了卤素和/或络合作用对选择性和还原能力的影响。(4)以烯丙基阴离子、氢负离子和乙烯基阴离子为配位体合成了高配位硅化合物。例如，烯丙基硅烷经历烯丙基化或[2+2]环加成，这取决于受体（细尾）。(5)为了研究14族元素化合物作为碳亲核试剂的能力，合成了含氮双环锗和锡化合物。发展了钯催化的卤代化合物偶联反应，并将其应用于天然产物（Migita）的合成。(6)合成了五配位的有机锑铋化合物，并通过X-射线晶体学分析确定了它们的结构。这些化合物的假旋转被亲核试剂如氟离子（Yamamoto）加速。

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).