Development of Synthetic Methods for the Silaallene Cationic Species and the Related Compounds and Their Application Reactions

硅杂烯阳离子及其相关化合物的合成方法及其应用反应的进展

• 批准号: 16390008
• 负责人: NAGAO Yoshimitsu
• 金额: $ 9.28万
• 依托单位: The University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16390008/
• 关键词: silaallene; diarylmonoalkynylfluorosilane; dialkynyldiarylsilane; oxasiletane; azasiletane; silacyclobutene; desilylation; conjugated diene; シラレン; シラアレンカチオン; ジアリルアルキニルフルオロシラン; ジアリルジアルキニルシラン; テトラクロロシラン; ジアリルジフルオロシラン; X線結晶構造解析; テトラフルオロシラン; ア

First, we have developed highly efficient synthetic methods for diarylmonoalkynylfluorosilanes and dialkynyldiarylsilanes as follows. Reaction of aryllithiums with tetrachlorosilane gave monoaryltrichlorosilanes, which were treated with other aryllithiums to afford diaryldichlorosilanes. After halogen exchange reaction (Cl→F), treatment of the resulting diaryldifluorosilanes with alkynyllithiums gave the desired diarylmonoalkynylfluorosilanes. Their similar reactions with other alkynyllithiums furnished the corresponding alkynyl-substituted dialkynyldiarylsilanes in excellent yields. Treatment of the monoalkynylmonoarylfluorosilane bearing t-Bu, Tip, phenylalkynyl, and fluorine atom with t-BuLi at 0℃ and then at room temperature or under reflux generated a 1-silaallene. The 1-silaallene was in situ allowed to react with ketones, aldehydes, and an imine to give the corresponding 1,2-oxasiletanes and 1,2-azasiletane, respectively. Treatment of the differrent kinds of alkynyl-substituted dialkynyldiarylsilanes with biscyclopentadienylzirconocene-ethylene complex followed by acidification with 3N HC1 gave regio-and stereoselectively the corresponding silacyclobutenes in good yields. Desilylation of the silacyclobutenes with tetrabutylammonium fluoride afforded stereoselectively unsymmetrical conjugated dienes and trienes in excellent yields, respectively.

首先，我们开发了二芳基单炔基氟硅烷和二芳基二芳基硅烷的高效合成方法如下。芳基锂与四氯硅烷反应得到单芳基三氯硅烷，再与其他芳基锂反应得到二芳基二氯硅烷。卤素交换反应（Cl→F）后，用炔基锂处理生成二芳基二氟硅烷，得到所需的二芳基单炔基氟硅烷。它们与其他炔基锂类似的反应，得到相应的炔基取代二炔基二烷基硅烷，产率高。将含t-Bu、Tip、苯炔基和氟原子的单炔基单芳基氟硅烷用t-BuLi在0℃下处理，然后在室温下或回流下生成1-硅烯。1-硅烯在原位与酮类、醛类和亚胺反应，分别生成相应的1,2-草硅烷和1,2-氮硅烷。用双环戊二烯锆-乙烯配合物处理不同种类的烷基取代二炔基二芳基硅烷，然后用3N HC1酸化，得到相应的区域选择性和立体选择性的硅环丁烯，收率高。四丁基氟化铵对硅环丁烯进行脱硅反应，得到立体选择性非对称共轭二烯和三烯，收率高。

项目成果

Expeditious Syntheses of Conjyugated Allenyl Esters and Oxazoles through a Cascade Reaction of α-Alkynyl Malonates under Alkaline Conditions

碱性条件下通过 α-丙二酸炔基酯的级联反应快速合成共轭烯基酯和恶唑

• 发表时间: 2006
• 期刊: Chemical & Pharmaceutical Bulletin 54・2
• 作者: 吉原利一;他;Yoshimitsu Nagao
• 通讯作者: Yoshimitsu Nagao

New ring-expansion reactions of hydroxy propenoyl cyclic compounds under palladium(0)/phosphine-catalyzed conditions.

• DOI: 10.1021/ol049450c
• 发表时间: 2004-05
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Y. Nagao;Satoru Tanaka;A. Ueki;Masunori Kumazawa;S. Goto;T. Ooi;S. Sano;M. Shiro

Preferential Conformation of the Six-membered Cyclic Compounds Bearing Both Trimethyl-siloxy(or Methoxymethyleneoxy) and Tributyistannyl Groups at the Geminal Position

双位同时带有三甲基硅氧基（或甲氧基亚甲氧基）和三丁锡烷基的六元环状化合物的择优构象

• 发表时间: 2004
• 期刊: Heterocycles 62
• 作者: Tatara Y;et. al.;Yoshimitsu Nagao
• 通讯作者: Yoshimitsu Nagao

Facile Generation Method for Conjugated Allenyl Esters Based on retro-Dieckmann Type Ring-Opening

基于逆迪克曼型开环的共轭烯基酯的简易生成方法

• 发表时间: 2005
• 期刊: Tetrahedron Letters 46・16
• 作者: 後藤文之;他;Yoshimitsu Nagao
• 通讯作者: Yoshimitsu Nagao

New Synthetic Methods for Seven-and Eight-Membered Cyclic Ethers Based on the Ring-Expansion Reactions of Hydroxy or Lithioxy Methoxyallenylisochroman Derivatives

基于羟基或锂硫氧基甲氧基联烯基异色满衍生物扩环反应的七元和八元环醚合成新方法

• 发表时间: 2004
• 期刊: Synlett 3
• 作者: Tatara Y;Namba T;Yamagata;Y.;Yoshida;T;Uchida;T. and Ichishima;E;Yoshimitsu Nagao et al.
• 通讯作者: Yoshimitsu Nagao et al.