Fundamental Research of Reactivity and Usage of Reagents Fluorine

氟试剂的反应性及用途基础研究

• 批准号: 11650847
• 负责人: HORI Kenzi
• 金额: $ 1.98万
• 依托单位: Yamaguchi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650847/
• 关键词: fluorine compounds; Ab initio MO calculation; Density Functional method; S_N1-like mechanism; DAST; selective methylation; sp^2 carbon; fluorination; 付加脱離機構; 活性化エネルギー

Fluorine compounds have been useful intermediates for organic synthesis in recent years. However, many difficulties in treating the F atom within theoretical method prevent the method from widely use for investigating mechanism of reactions with the atom. In the present study, we used ab intio molecular orbital calculations as well as the Density Functional theory, whose efficiency for the fluorine compounds was proved recently, were used to calculate physico-chemical property and the reaction mechanisms of unique fluorine compounds. We performed following investigations (1) A new usage of DAST for selective methylation of 2-hydroxypyrimidine using trimethyl-silyldiazomethane, (2) Theoretical Study of Fluorination mechanism of 2-hydroxy-3-phenylalkinate with DAST,(3) Ab initio Molecular orbital study on three feasible mechanisms for substitution of the vinyl carbon in F_2C=C(OMs)BMe_3^-, (4) Ab initio molecular orbital study on substitution on the vinylic carbon in F_2C=C(OMs)BMe_3^- under S_N1-like mechanism. The former two studies intended to prove unique properties of DAST(diethylaminosulfur hifluoride), a famous fluorination reagent. The Density Functional calculations showed that the reaction of DAST and H_2O produces a strong acid which is the key for selective methylation of 2-hydroxypyrimidine. The latter two were dedicated to clarify the mechanisms of substitution reactions on the sp^2 carbon in a fluorine compound, F_2C=C(OMs)BMe_3^-. The present study achieved the initial purpose sufficiently.

氟化合物是近年来有机合成中常用的中间体。然而，理论方法在处理F原子方面的许多困难阻碍了该方法在研究与F原子反应机理方面的广泛应用。在本研究中，我们采用从头算分子轨道计算和密度泛函理论计算了特殊氟化合物的物理化学性质和反应机理，密度泛函理论对氟化合物的效率最近得到了证明。我们进行了以下研究：(1)DAST在三甲基硅基重氮甲烷选择性甲基化2-羟基嘧啶中的新应用；(2)DAST对2-羟基-3-苯基酸盐氟化机理的理论研究；(3)从头算分子轨道研究了F_2C=C(OMs)BMe_3^-中乙烯基碳取代的三种可行机制；(4)从头算分子轨道研究了F_2C=C(OMs)BMe_3^-中乙烯基碳在s_n1类机制下的取代机理。前两项研究旨在证明著名的氟化试剂DAST（二乙基氨基硫氟化）的独特性质。密度泛函计算表明，DAST与H_2O反应产生的强酸是2-羟基嘧啶选择性甲基化的关键。后两者致力于阐明氟化合物F_2C=C(OMs)BMe_3^-中sp^2碳的取代反应机理。本研究充分达到了最初的目的。

项目成果

Shohei Fukuda, Shinsuke Yamato, Kenzi Hori: "Theoretical Study of Fluorination mechanism of 2-hydroxy-3-phenylalkinate with DAST."J.Computer Aided Chemistry. 1. 47-56 (2000)

Shohei Fukuda、Shinsuke Yamato、Kenzi Hori：“用 DAST 对 2-羟基-3-苯基烷基酯的氟化机理进行理论研究。”J.计算机辅助化学。

Kenzi Hori: "Ab Inifio Molecular Orbital Study of Substitution on the Vinylic Ceulion in F_2C=(10Ms)Bmej under sol-like Mechanism"JCPE Journal. 11. 23-28 (1999)

Kenzi Hori：“类溶胶机制下 F_2C=(10Ms)Bmej 中乙烯基 Ceulion 取代的从头开始分子轨道研究”JCPE 杂志。

Kenzi Hori, Shohei Fukuda, Junji Ichikawa: "Ab Initio Molecular Orbital Study on Three Feasible Mechanisms for Substitution of the Vinylic Carbon in F_2C=C(OMs)BMe_3^-."Tetrahedron. 55. 14915-14924 (1999)

Kenzi Hori、Shohei Fukuda、Junji Ichikawa：“从头开始分子轨道研究 F_2C=C(O​​Ms)BMe_3^- 中乙烯基碳取代的三种可行机制。”四面体。

K.Hori, S.Fukuda, Y.Kawano, J.Ichikawa: "Ab Initio Molecular Orbital Study of Substitution on the Vinylic Carbon in F_2C=C(OMs)BMe_3^- under S_N1-like Mechanism."JCPE Journal. 11. 23-28 (1999)

K.Hori、S.Fukuda、Y.Kawano、J.Ichikawa：“类 S_N1 机制下 F_2C=C(O​​Ms)BMe_3^- 中乙烯基碳取代的从头分子轨道研究。”JCPE 杂志。

Kenzi Hori: "Ab Inifio Molecular Orbital Study in Three Feasible Mechanism for Substitution of the Vinylic Ceulion in F_2C=(10Ms)Bmej"Tetrahedron. 55. 10915-14924 (1999)

Kenzi Hori：“从头开始分子轨道研究替代 F_2C=(10Ms)Bmej 中乙烯基 Ceulion 的三种可行机制”四面体。