Chemoselective Transformation of C-C Double Bonds by Using Transition-Metal Hediated Electrolysis

过渡金属辅助电解化学选择性转化 C-C 双键

• 批准号: 08651011
• 负责人: KUROBOSHI Manabu
• 金额: $ 1.41万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08651011/
• 关键词: Olefin; Oxidation; Electrolysis; Ruthenium; Osmium; Asymmetric Induction; Natural Product; ジヒドロキシル化; アミノヒドロキシル化

In this project were investigated dihydroxylation and aminohydroxylation of carbon-carbon double bonds using transition-metal catalysts.Chiral diols were obtained from asymmetric electro-dihydroxylation of olefins using osmium and chiral ligands in the presence of a catalytic amount of potassium ferricyanide or iodine. This method was applied to the synthesis of chiral Shikonin. Effects of intramolecular hetero-atom on chiral induction was also studied.N,N-Dichloro-p-toluenesulfonamide was obtained from electrolysis of p-sulfonamide in aq. NaCl. The dichlorinated sulfonamide was easily hydrolyzed with a basic aqueous solution to give N-chloro-p-toluenesulfonamide. Asymmetric aminohydroxylation of olefins using the chlorinated p-toluenesulfonamide in the presence of chiral osmium catalyst proceeded smoothly to give chiral aminols in moderate yields and ees.

本项目研究了过渡金属催化剂对碳碳双键的二羟基化和氨羟基化反应，在催化量的铁氰化钾或碘的存在下，利用锇和手性配体对烯烃进行不对称电二羟基化反应，得到手性二醇。将该方法应用于手性紫草素的合成。研究了分子内杂原子对手性诱导的影响。氯化钠。二氯磺酰胺在碱性水溶液中易水解生成N-氯对甲苯磺酰胺。在手性锇催化剂存在下，用氯化对甲苯磺酰胺进行烯烃的不对称氨羟化反应，以中等的产率和ee顺利地得到手性氨基醇。

项目成果

T.Hase,M.Kuroboshi,T.Katagiri S.Torii,C.Amatore,A.Jutand,H.: "A Facile Synthesis of Biradical Compounds Containing Two N-oxyl Groups Connected with Conjugated π-System" Tetrahedron hett.38. 7391-7394 (1997)

T. Hase、M. Kuroboshi、T. Katagiri S. Torii、C. Amatore、A. Jutand、H.：“含两个与共轭 π 系统相连的 N-氧基团的双自由基化合物的简便合成” 四面体 hett.38 .7391-7394 (1997)

A.Jutand,H.Kawafuchi,C.Amatore,M.Kuroboshi,S.Torii: "A Consideration of Mechanism of Tin-Medistool Electron Allylation of Canbonyl Compounds" Novel Treads in Electroorganic Synthesis. 349-350 (1998)

A.Jutand，H.Kawafuchi，C.Amatore，M.Kuroboshi，S.Torii：“对 Canbonyl 化合物的锡-Medistool 电子烯丙基化机制的考虑”有机电合成中的新进展。

S.Torii,T.Hase,M.Kuroboshi,T.Katagiri,C.Anatore,A.Jutand,H.Kawafuchi: "Synthesis of Terminal-Biradical Compounds Consisting of Two N.Oxyl Groups Connected with Conjugated π-System" Novel Trends in Electroorganic Sythesis. 87-88 (1998)

S.Torii、T.Hase、M.Kuroboshi、T.Katagiri、C.Anatore、A.Jutand、H.Kawafuchi：“由两个与共轭 π 系统连接的 N.Oxyl 基团组成的末端双自由基化合物的合成”小说有机电合成的趋势。87-88 (1998)

HASE Tomoyuki, KUROBOSHI Manabu, KATAGIRI Toshimasa, TORII Sigeru, AMATORE Christian, JUTAND Anny, KAWAFUCHI Hiroyuki: "A Facile Synthesis of Biradical Compounds Containing Two N-Oxyl Groups Connected with Conjugated pi-System" Tetrahedron Lett.38. 7391-7

HASE Tomoyuki、KUROBOSHI Manabu、KATAGIRI Toshimasa、TORII Sigeru、AMATORE Christian、JUTAND Anny、KAWAFUCHI Hiroyuki：“包含与共轭 pi 系统连接的两个 N-氧基团的双自由基化合物的简便合成”Tetrahedron Lett.38。

M.Kuroboshi,M.Tanaka,S.Kishimoto,H.Tanaka,S.Torii: "Electrochemical Regeneration of Chromium (II).Alkenylation of Carbonyl Compounds" Synlett. 69-70 (1999)

M.Kuroboshi、M.Tanaka、S.Kishimoto、H.Tanaka、S.Torii：“铬 (II) 的电化学再生。羰基化合物的烯基化”Synlett。