Synthesis and Reactions of Strucuturally New Intermediates of the Witting-type Reactions Contaning Group 13,14, and 15 Elements

含13,14,15族元素的新型Witting型反应中间体的合成与反应

• 批准号: 07454160
• 负责人: KAWASHIMA Takayuki
• 金额: $ 5.06万
• 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 (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454160/
• 关键词: Tetracoordinate 1,2-oxaboretanide; Pentacoordinate 1,2-oxagermetanide; Spirobi[1,2-oxaboretanide]; Pentacoordinate 1,2-azaphosphetidine; Witting-type reaction; X-ray crystallographic analysis; Trigonal bipyramidal structure; Isomerization; 二分子オレフィ

1.The first tetracoordinate 1,2-oxaboretanide has been synthesized by treatment of the corresponding beta-hydroxyalkyldimesitylborane with KH in the presence of 18-crown-6. The X-ray crystallographic analysis has shown that it has a distorted tetrahedral structure. Thermolysis has given the corresponding olefin, indicating that it is an intermediate of the boron-Witting reaction. On heating trimethylsilyl ether of benzaldehyde adduct undergoes the Witting-type reaction to give the corresponding olefin. 2.A pentacoordinate 2-Phenyl-1,2-oxagermetanide bearing the Martin ligand has been similarly obtained from the corresponding beta-hydroxyalkylgermane as an intermediate of the germanium-Peterson reaction. 2-Methyl derivative has also been given. The X-ray crystallographic analysis has shown that they have a distorted trigonal bipyramid (TBP) structure. Before olefin formation reaction takes place, thermal isomerization has been observed for both 2-phenyl and 2-methyl-1,2-oxagermetanides, kinetic study indicating that the isomerization proceeds via a different mechanism each other. 3.2,2,6,6-Tetraphenyl-and 2,2,6,6-tetrakis(p-chlorophenyl)-1,5-dioxa-4lambda^5-phoshaspiro[3.3]heptanes have been synthesized by the cyclization and dehydration reaction of the corresponding dihydroxyphosphine oxides with Appel reagent (Ph_3P-CCI_4). Although they not isolable, three diastereomers of 3,7-dimethyl derivative of the latter have been isolated. The X-ray crystallographic analysis has shown that two diastereomers have a distorted TBP structure, but one has a distorted tetragonal pyramid structure. Their thermolysis has given two molar equivalents of the corresponding olefin. The first example of pentacoordinate 1,2-azaphosphetidines has also been synthesized and C-apical and N-equatorial pseudorotamer has been observed for the first time. These results have been partially published as short communications.

1.在18-冠-6的存在下，用KH与相应的-羟基烷基聚乙基硼烷反应，合成了第一个四配位的1,2-氧硼烷。x射线晶体学分析表明其具有扭曲的四面体结构。热裂解得到相应的烯烃，表明它是硼-威廷反应的中间产物。加热苯甲醛加合物三甲基硅醚，发生威廷型反应生成相应的烯烃。2.同样，作为锗-彼得森反应的中间体，从相应的β -羟基烷基日耳曼中得到了含马丁配体的五配位2-苯基-1,2-氧agermetanide。也给出了2-甲基衍生物。x射线晶体学分析表明，它们具有扭曲的三角双棱锥结构。在烯烃生成反应发生之前，2-苯基和2-甲基-1,2-氧agermetanides都观察到热异构化，动力学研究表明异构化是通过不同的机制进行的。用Appel试剂（Ph_3P-CCI_4）对相应的二羟基膦氧化物进行环化脱水反应，合成了3.2,2,6,6-四苯基和2,2,6,6-四基（对氯苯基）-1,5-二氧基-4 λ ^5-磷斯匹罗[3.3]庚烷。3,7-二甲基衍生物的三个非对映体虽不能分离，但已被分离出来。x射线晶体学分析表明，两种非对映体具有畸变的TBP结构，而一种具有畸变的四方金字塔结构。它们的热分解反应得到两个摩尔当量的相应烯烃。合成了首个五坐标1,2-氮杂磷脂的例子，并首次观察到c -尖和n -赤道的假旋聚体。这些结果部分以简短的通讯形式发表。

项目成果

T.Kawashima: "Synthesis,Structure,and Thermolysis of N-Apical 1,2λ^5-Azaphosphetidines with a Pentacoordinate P Center and the First Observation of Their N-Equatorial Pseudorotamers" Angew.Chem.,Int.Ed.Engl.33. 1097-1098 (1996)

T.Kawashima：“具有五配位 P 中心的 N-Apical 1,2λ^5-Azaphosphetidines 的合成、结构和热解以及其 N-Equatorial Pseudorotamers 的首次观察”Angew.Chem.,Int.Ed.Engl.33 .1097-1098 (1996)

T.Kawashima: "Synthesis and Thermolysis of Hexacoordinate 1,2-Oxaphosphetanides" Tetrahedron Lett.((in press))

T.Kawashima：“六配位 1,2-Oxaphosphetanides 的合成和热解”Tetrahedron Lett.（（正在印刷中））

T.Kawashima, N.Yamashita, and R.Okazaki: "Thermolysis of beta-Siloxyalkylboranes : Formation of Alkenes and/or Silyl Enol Ethers." Chem.Lett.1107-1108 (1995)

T.Kawashima、N.Yamashita 和 R.Okazaki：“β-硅氧基烷基硼烷的热解：烯烃和/或硅烯醇醚的形成”。

T.Kawashima, T.Soda, and R.Okazaki: "Synthesis Structure, and Thermolysis of N-Apical 1,2lambda^5-azaphosphetidines with a pentacoordinate P Center and the First Observation of Their N-Equatorial Pseudorotamers" Angew.Chem., Int.Ed.Engl.35. 1096-1098 (199

T.Kawashima、T.Soda 和 R.Okazaki：“具有五配位 P 中心的 N-Apical 1,2lambda^5-azaphosphetidines 的合成结构和热解以及其 N-赤道假旋转异构体的首次观察” Angew.Chem。

T.Kawashima: "Synthesis,Structure,and Thermolysis of a Tetracoordinate 1,2-Oxaboretanide : An Intermediate of the Boron-Wittig Reaction under Basic Conditions" J.Am.Chem.Soc.117. 6142-6143 (1995)

T.Kawashima：“四配位 1,2-Oxaboretanide 的合成、结构和热解：基本条件下硼-Wittig 反应的中间体”J.Am.Chem.Soc.117。