New Method of Radical Formation and Its Application to Organic Synthesis

自由基形成新方法及其在有机合成中的应用

• 批准号: 63470074
• 负责人: UTIMOTO Kiitiro
• 金额: $ 4.99万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470074/
• 关键词: Radical; Triethylborane; Triphenystannane; Addition; Cyclization; Triphenylgermane; Acetylene; Alkyl iodide; 付加反応; ヨウ化ビニル; ヨウ化ペルフルオロアルキル; ラジカル付加; αーハロケトン; ビニルシクロプロパン転位; パラジウム触媒

Novel efficient method for the generation of organic radical species has been applied to organic syntheses. Triethylborane-initiated addition of triphenylstannane to acetylenes proceeds smoothly in high regio- and stereoselectivity. Application to an acetylene containing an olefinic bond at appropriate position provides a cyclized product stereoselectively; triphenyltin radical attacks at acetylene bond regioselectively to give a vinyl radical, which adds intramolecularly to an olefin stereoselectively. Triphenylgermane adds to a 1-alkyne under triethylborane catalysis. In this case, reaction is kinetically controlled at -78ﾟC to give Z-isomer, whereas reaction is thermodynamically controlled at 60ﾟC affording Enisomer predominantly. By the mechanistic investigation of the above reaction, an efficient procedure of the isomerization of olefin geometry has been devised. Alkyl halides can be reduced to the corresponding hydrocarbons by radical type reduction. Intramolecular addition of alkoxythiocarbonyl radical, an acyl radical equivalent, gives an -methylene lactone. Alkyl iodides add to acetylene smoothly under triethylborane catalysis to give vinyl iodides regio- and stereoselectively. Perfluoroalkyl iodides add to acetylenes analogously. Reaction of an -bromo ketone with a carbonyl compound in the presence of triethylborane gives a Reformatsky type reaction product; formation of boron enolate and reaction with aldehyde to give an aldol product. Triethylborane-mediated addition of an alkyl iodide to methyl vinyl ketone also gives a boron enolate. As the obtained boron enolate reacts with an aldehyde to give aldol product, the above reactions opens novel three components coupling reaction of alkyl iodide, methyl vinyl ketone, and aldehyde.

有机自由基物种的产生方法已被应用于有机合成中。三乙基硼烷引发的三苯基锡烷与乙炔的加成反应具有很高的区域和立体选择性。应用于在适当位置含有烯键的乙炔提供立体选择性的环化产物;三苯基锡自由基区域选择性地攻击乙炔键以产生乙烯基自由基，其立体选择性地分子内加成到烯烃上。三苯基锗烷在三乙基硼烷催化下与1-炔加成。在这种情况下，反应动力学控制在-78 ° C，得到Z-异构体，而反应动力学控制在60 ° C，主要得到烯异构体。通过对上述反应机理的研究，设计了一种有效的烯烃几何异构化方法。卤代烷可以通过自由基型还原反应被还原成相应的烃。分子内加成烷氧硫代羰基（酰基等价物），得到-亚甲基内酯。在三乙基硼烷催化下，碘代烷与乙炔顺利地加成，区域和立体选择性地生成碘代乙烯。全氟烷基碘类似地与乙炔加成。在三乙基硼烷存在下，α-溴代酮与羰基化合物反应，得到Reformatsky型反应产物;形成硼烯醇化物，并与醛反应，得到羟醛产物。三乙基硼烷介导的烷基碘与甲基乙烯基酮的加成也得到硼烯醇化物。由于所得烯醇化硼与醛反应生成羟醛缩合产物，上述反应开辟了烷基碘、甲基乙烯基酮和醛的新的三组分偶联反应。

项目成果

三浦勝清: "Triethylborane-Induced Hydrodehalogenation of Organic Halides by Tin Hydrides" Bull.Chem.Soc.Jpn.62. 143-147 (1989)

Katsukiyo Miura：“三乙基硼烷诱导的锡氢化物对有机卤化物的加氢脱卤”Bull.Chem.Soc.Jpn.62 (1989)。

NOZAKI, Kyoko: "Facile Routes to Boron Enolates. Et_3B-Mediated Reformatsky Type Reaction and Three Components Coupling Reaction of Alkyl Iodides, Methyl Vinyl Ketones and Carbonyl Compounds" Tetrahedron Letters, 29, 1041-1044, 1988.

NOZAKI, Kyoko：“硼烯醇化物的简便路线。Et_3B 介导的 Reformatsky 型反应和烷基碘、甲基乙烯基酮和羰基化合物的三组分偶联反应”《四面体快报》，29, 1041-1044, 1988。

ICHINOSE, Yoshifumi: "Et_3B-Induced Radical Reaction of 1,3-Diene Monoxide with C_6F_<13>I, PhSH, or Ph_3GeH" Chemistry Letters, 1437-1440, 1988.

ICINOSE，Yoshifumi：“Et_3B 诱导的 1,3-二烯一氧化物与 C_6F_13>I、PhSH 或 Ph_3GeH 的自由基反应”化学快报，1437-1440，1988。

MIURA, Katsukiyo: "Synthesis of Vinylcyclopentanes from Vinylcyclopropanes and Alkenes Promoted by Benzenethiyl Radical" Tetrahedron Letters, 29, 5135-5138, 1988.

MIURA, Katsukiyo：“由苯乙基自由基促进的乙烯基环丙烷和烯烃的乙烯基环戊烷的合成”，四面体快报，29, 5135-5138, 1988。

MIURA, Katsukiyo: "Triethylborane-Induced Hydrodehalogenation of Organic Halides by Tin Hydrides" Bull. Chem. Soc. Jpn. 62, 143-147, 1989.

MIURA，Katsukiyo：“三乙基硼烷诱导锡氢化物对有机卤化物的加氢脱卤”公牛。