Stereoselective Cyclization Reactions Using Organotin Compounds

使用有机锡化合物的立体选择性环化反应

• 批准号: 63550616
• 负责人: YAMAMOTO Makoto
• 金额: $ 1.09万
• 依托单位: Chiba University, Faculty of Engineering
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 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/grant/KAKENHI-PROJECT-63550616/
• 关键词: Organotin Compound; LTA Cyclization; Radical Cyclization; Epoxy-allylic Tin Compound; Thionolactone Synthesis; Stereoselective Cyclization; Tandem Cyclization; 立体選択的環化反応

The following results were obtained from the study of "Stereoselective Cyclisation Reactions Using Organotin Compounds".1). By the oxidative substitution reactions of organotin compounds with LTA gave corresponding oxygen-functionalized one. This oxidation was applied to the synthesis of 4-ylidenebutenolides. Treatment of 5-stannyl-1,3-pentandiol derivatives with LTA gave 4-hydroxytetrahydropyran in good yield. The diol which has a double or a triple bonds in its molecule were further cyclized to a polycyclic ether. The cyclization of 3-hydroxy-5-stannyl- pentanoic acid yielded 4-hydroxy-delta-lactone.2). The radical cyclization of xanthates using tri-n-butyltin hydride gave a thionolactone which was easily oxidized to its lactone. The diastereo- selectivity of the cyclization was well controlled (de> 95%). The linear xanthates having two kinds of radical acceptor sites also cyclized to multifused thionolactone (Tandem radical cyclization).3). Lewis-acid induced regio- and stereoselective cyclization of epoxy-allylic stannanes was also carried out. The cyclization proceeded in good yield, and the regioselectivity of the cyclization was governed by the stability of the carbocation which was formed. The stereochemistry around the epoxide carbons was also discussed.

以下结果是从“使用有机锡化合物的立体选择性环化反应”的研究中获得的。1)。通过有机锡化合物与LTA的氧化取代反应，得到相应的氧官能化化合物。该氧化被应用于4-亚基丁烯内酯的合成。用LTA处理5-甲锡烷基-1,3-戊二醇衍生物，以良好的收率得到4-羟基四氢吡喃。分子中具有双键或三键的二醇进一步环化为多环醚。 3-羟基-5-甲锡烷基-戊酸环化产生4-羟基-δ-内酯。2)。使用三正丁基氢化锡对黄原酸酯进行自由基环化，得到硫代内酯，该硫代内酯很容易被氧化为其内酯。环化的非对映选择性得到很好的控制(de>95%)。具有两种自由基受体位点的直链黄原酸酯也环化为多稠合硫醇内酯（串联自由基环化）。3)。还进行了路易斯酸诱导的环氧烯丙基锡烷的区域选择性和立体选择性环化。环化以良好的产率进行，并且环化的区域选择性由所形成的碳阳离子的稳定性控制。还讨论了环氧化物碳的立体化学。

项目成果

山本忠: 有機合成化学協会誌. 46. 1134-1148 (1988)

山本正：合成有机化学学会杂志 46。1134-1148 (1988)

M. Yamamoto, T. Uruma, S. Kohmoto and K. Yamada: "Regioselective Synthesis of 4-Alkylidenbutenolides" Nippon Kagaku Kaishi, 1989, 760-763.

M. Yamamoto、T. Uruma、S. Kohmoto 和 K. Yamada：“4-Alkylidenbutenolides 的区域选择性合成”Nip​​pon Kagaku Kaishi，1989，760-763。

M.Yamamoto: "Tri-n-butyltin Hydride Assisted Highly Stereoselective Lactonisation of Homoallylic Xanthates" J.Chem. Soc.,Chem.Commun.,. 1989. 1265-1266 (1989)

M.Yamamoto：“三正丁基氢化锡辅助同烯丙基黄原酸盐的高度立体选择性内酯化”J.Chem。

M.Yamamoto: J.Chem.Soc.,Chem.Commun.1988. 560-561 (1988)

M.Yamamoto：J.Chem.Soc.，Chem.Commun.1988。

M.Yamamoto: "Oxidative Substitution Reactions of Olefinic Tin Compounds with Lead Tetra-acetate" Chem.Lett.,. 1989. 221-222 (1989)

M.Yamamoto：“烯属锡化合物与四乙酸铅的氧化取代反应”Chem.Lett.，。