Development of Novel Type Reactions of Organotin Compounds Directed towards Organic Synthesis

针对有机合成的新型有机锡化合物反应的发展

• 批准号: 03453033
• 负责人: SATO Tadashi
• 金额: $ 4.35万
• 依托单位: Waseda 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: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453033/
• 关键词: Organotin Compound; Double Anion; Organic Synthesis; βスタンニルケトン; γスタンニルケトン; アルキル転位; ルイス酸

Because of the electropositive character of the tin atom compared with that of carbon atom, the tin-carbon bond exhibits its reactivity as a carbanion. Since the unprovoked tin-carbon bond is so stable, however, no obvious interference with reactive functional groups is expected during the reaction with other substrates, thus allowing us to prepare tin-containing compounds having various functionalities within the same molecule. Upon manipulating the tin-carbon bond in the second-stage reaction, we can reallize novel types reactions typical of the tin-compounds, which are applicable for the synthetic purpose.The reagent depicted by I and II can be viewed as double anion (III) or anion/cation (IV) equivalents. We have developed new tin-containing reagents 1-4 as useful synthetic reagents. The reaction types of the tin compounds thus prepared are dependent upon (1) the nature of the functional groups within the same molecule, (2)the method of the activation of the functional groups, (3)relative distance between tin-carbon bond and the functional groups, and (4)the presence of the auxiliary groups. Utilizing these characteristics, we developed novel types reactions (6)-(8), and applied these reactions for the synthesis of some natural products.

由于与碳原子相比，锡原子的电阳性特征，锡碳键表现出其反应性作为carbanion。但是，由于无端的锡碳键是如此稳定，因此在与其他底物的反应过程中没有明显的干扰反应性官能团，从而使我们能够制备具有同一分子内各种功能的含TIN的化合物。在操纵二阶段反应中的锡碳键后，我们可以重新化锡型化合物的典型新型类型反应，这适用于合成目的。I和II所描述的试剂可以视为双阴离子（III）（III）或阴离子/阳离子（IV）等效。我们已经开发了新的含锡的试剂1-4作为有用的合成试剂。这样制备的锡化合物的反应类型取决于（1）官能团在同一分子中的性质，（2）官能团的激活方法，（3）锡 - 碳键和官能团之间的相对距离，以及（4）辅助组的存在。利用这些特征，我们开发了新型的反应（6） - （8），并将这些反应应用于某些天然产物的合成。

项目成果

T.Sato,M.Hayashi,and T.Hayata: "Lewis Acid-induced Reaction of Silicon-containing Stannyl Ketones and Its Application to the Synthesis of(+)-β-Cuparenone" Tetrahedron,48,4099-4114(1992).48. 4099-4114 (1992)

T.Sato、M.Hayashi 和 T.Hayata：“路易斯酸诱导的含硅甲锡烷基酮反应及其在 (+)-β-Cuparenone 合成中的应用” 四面体，48,4099-4114(1992) .48.4099-4114（1992）

J.Fujiwara and T.Sato: "Dependence of the Lewis Acid-Induced Reaction of beta-Stannyl Ketones upon Substitution Pattern : Cyclopropanation versus 1,2-Alkyl Migration" Bull, Chem.Soc.Jpn. 66. 1258-1264 (1993)

J.Fujiwara 和 T.Sato：“β-甲锡烷基酮的路易斯酸诱导反应对取代模式的依赖性：环丙烷化与 1,2-烷基迁移”Bull，Chem.Soc.Jpn。

T.Sato, T.Kikuchi, H.Tsujita, A.Kaetsu, N.Sootome, K.Nishida, K.Tachibana, E.Murayama: "The Reaction of Trialkylstannylmethyllithium with alpha, beta-Epoxy Ketones and alpha-Chloro Ketones" Tetrahedron. 47. 3281-3304 (1991)

T.Sato、T.Kikuchi、H.Tsujita、A.Kaetsu、N.Sootome、K.Nishida、K.Tachibana、E.Murayama：“三烷基甲锡烷基甲基锂与 α、β-环氧酮和 α-氯酮的反应”

T.Sato, A.Kawase, and T.Hirose: "Tributylstannylcarbinylzinc as an Alkylideno Double Anion Equivalent" Synlett.891-892 (1992)

T.Sato、A.Kawase 和 T.Hirose：“三丁基甲锡烷基锌作为亚烷基双阴离子等效物”Synlett.891-892 (1992)

J.Fujiwara,M.Watanabe,and T.Sato: "Diversity in the Lewis Acid-induced Reaction of Aldehydes with γ-Substituted Allylstannanes Depending upon the Types of the Substituents" J.Chem.Soc.,Chem.Comm,1994,349-351.349-351 (1994)

J.Fujiwara、M.Watanabe 和 T.Sato：“醛与 γ-取代的烯丙基锡烷在路易斯酸诱导反应中的多样性取决于取代基的类型”J.Chem.Soc.，Chem.Comm，1994， 349-351.349-351 (1994)