Design of Innovative Ligands and Their Utilization for the Synthesis of Novel Highly Coordinate Organoheteroatom Compounds

创新配体的设计及其在新型高度配位有机杂原子化合物合成中的应用

• 批准号: 12304037
• 负责人: KAWASHIMA Takayuki
• 金额: $ 29.4万
• 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 (A)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12304037/
• 关键词: tricoordinate 1,2-iodoxetane; T-shaped iodane structure; tetradentate ligand; anti-apicophilic structure; 5-carbaphosphatrane; dendrimer-type substituent; pentacoordinate difluorosilicate; X-ray crystallographic analysis; m-テルフェニルユニット; 5配位トリフルオロシ

1. A tricoordinate 1,2-iodoxetane was successfully synthesized by oxidative cyclization of (Z)-1,1,1,6,6,6-hexafluroro-3-iodo-2,5-bis(trifluoromethyl)-3-hexene-2,5-diol with t-BuOCl. X-ray crystallographic analysis showed that this compound has a pseudo trigonal bipyramidal structure with two oxygen atoms at the apical positions and one carbon atom and two lone pairs at the equatorial positions, which is classified to a T-shaped iodane structure.2. 4,4',4"-tri(t-butyl)-2,2',2" trimethoxytriphenylmethanol (Ar_3COH) was prepared. Reduction of Ar_3COH with triethylsilane, followed by lithiation with n-BuLi and the reaction with PCl_3 gave the corresponding phosphinic acid Ar_3CP(O)HOH after hydrolysis. Demethylation of Ar_3CP(O)HOH with ISi(CH_3)_3 successfully gave the desired 1-hydro-5-carbaphosphatrane with a novel tetradentate ligand. X-ray crystallographic analysis revealed that this compound has perfectly anti-apicophilic structure with hydrogen and carbon atoms at the apical positions and three oxygen atoms at the equatorial positions.3. 2,2",6,6"-Tetramethyl-m-terphenyl-5'-yl bromide (DenBr) was prepared from 1,3,5-tribromo-2-iodobenzene. Lithiation of DenBr followed by the reaction with SiCl_4 gave Den_4Si, which was converted to Den_3SiF via Den_3SiOH and Den_3SiCl. Fluorination of Den_3F with KF in the presence of [2.2.2]cryptand afforded the corresponding pentacoordinate difluorosilicate K^+, [2.2.2]cryptand Den_3F_2Si^-. The present research project has been achieved successfully.

1.通过(Z)-1，1，1，6，6，6-hexafluroro-3-iodo-2，5-bis(trifluoromethyl)-3-hexene-2，5-diol与t-BuOCl的氧化环合反应，成功地合成了三配位的1，2-碘氧杂环己烷。X-射线单晶分析表明，该化合物为假三角双锥结构，在顶端有两个氧原子，赤道位置有一个碳原子和两个孤对碳原子，属于T型碘结构。合成了4，4‘，4“-三(叔丁基)-2，2’，2”三甲氧基三苯基甲醇(Ar_3COH)。用三乙基硅烷还原Ar_3COH，然后用n-BuLi锂化合，再与PCl_3反应得到相应的亚膦酸Ar_3Cp(O)HOH。Ar_3Cp(O)HOH与ISI(CH_3)_3的脱甲基化反应成功地合成了具有新型四齿配体的1-氢-5-碳磷杂环己烷。X-射线单晶分析表明，该化合物具有完美的反亲尖结构，氢原子和碳原子位于顶端，三个氧原子位于赤道位置。以1，3，5-三溴-2-碘苯为原料合成了2，2“，6，6”-四甲基-间三苯基-5‘-溴(DenBr)。溴化后与SiCl4反应生成了DEN_4Si，再经DEN_3SiOH和DEN_3SiCl转化为DEN_3SiF。在[2.2.2]络合物存在下，用KF氟化Den_3F，得到相应的五配位二氟硅酸盐K^+、[2.2.2]络合物和Den_3F_2Si^-。本研究项目已成功实现。

项目成果

N.Kano: "Synthesis of Four-and Five-membered Heterocycles Derived from an Iminophosphorane"Phosphorus, Sulfur, Silicon Relat. Elem.. 177(in press). (2002)

N.Kano：“从亚氨基正膦衍生的四元和五元杂环的合成”磷、硫、硅相关。

N.Kano: "The First Isolable Pentacoordinate 1,2λ^5-Azaphosphetine : Synthesis, X-ray Crystallographic Analysis, and Dynamic Behaviour"Chem. Commun.. 2096-2097 (2001)

N.Kano：“第一个可分离的五配位 1,2λ^5-Azaphosphetine：合成、X 射线晶体分析和动态行为”Chem. 2096-2097 (2001)

N.Kano: "A Disilane Containing Two Heptacoordinate Silicon Atoms : Synthesis and Structure of a Disilane Bearing Dithiocarboxylato Ligands"Angew. Chem., Int. Ed.. 40. 3450-3452 (2001)

N.Kano：“含有两个七配位硅原子的乙硅烷：带有二硫代羧基配体的乙硅烷的合成和结构”Angew。

T.Kawashima: "Synthesis and Structure of a Tricoodinate 1,2-Iodoxetane"Phosphorus, Sulfur, Silicon Relat. Elem.. 168-169. 141-144 (2001)

T.Kawashima：“三坐标1,2-碘环丁烷的合成和结构”磷、硫、硅相关。

N.Kano: "Synthesis and Structures of Azobenzenes Bearing Silyl, Germyl, and Stannyl Groups at 2-Position"Chem. Lett.. 338-339 (2001)

N.Kano：“2 位带有甲硅烷基、甲锗烷基和甲锡烷基的偶氮苯的合成和结构”Chem。