Development and Application of New Transformations of Organosulfur Compounds Utilizing Magnesium Amides

氨基镁有机硫化合物新转化的开发与应用

• 批准号: 07651032
• 负责人: KOBAYASHI Kazuhiro
• 金额: $ 1.41万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651032/
• 关键词: Magnesium amides; Sulfides; unsymmetrical dithioacetals; Sulfoxides; alpha-Sulfenylalkylation; Asymmetric synthesis; Pummerer reaction; Sulfonium ions; 還元; α-アミノアルデヒド; チオール

It was found that sulfoxides bearing hydrogens at the alpha-position only (RSOCH_2R^1) reacted with the tetramethylpiperidinomagnesium reagent, which was generated in situ by treatment of 2,2,6,6-tetramethylpiperidine with ethylmagnesium bromide in refluxing diethyl ether, at room temperature to produce the corresponding dithioacetals (RSCHR^1SR). The treatment of sulfoxides bearing hydrogens both at the alpha- and beta-positions (RSOCHR^1CHR^2R^3) with the magnesium amide was found to afford the corresponding vinyl sulfides (RSCR^1=CR^2R^3) accompanying the corresponding dithioacetals. The pathways leading to the products involving the formation of the sulfur stabilized carbonium ion intermediates were elucidated, and these reactions were extended to syntheses of a range of organosulfur compounds.The reaction of sulfoxides bearing alpha-hydrogen (s) (RSOCHR^1R^2) with the diisopropylaminomagnesium reagent, which was generated in situ by the treatment of diisopropylamine with an excess … More amount of appropriate Grignard reagents (R^3MgBr), resulted in the formation of the corresponding sulfides (RSCR^1R^2R^3). Optically active sulfides could be obtained up to 75% e.e. by using optically active sulfoxides or secondary amines.The (diisopropylamino) magnesium reagent, generated from diisopropylamine and ethylmagnesium bromide, was treated with thiols (R^4SH) prior to the interaction with sulfoxides bearing hydrogen (s) at the alpha-position (R^1SOCHR^2R^3) to afford unsymmetrical dithioacetals (R^1SCR^2R^3SR^4).The treatment of vinyl sulfoxides (PhSOCHR^1=CHR^2) with (dialkylamino) magnesium reagents, generated from secondary amines (R^3_2NH) and ethylmagnesium bromide, proved to give unsymmetrical beta- (N,N-dialkylamino) dithioacetals [(PhS) _2CHR^1CHR^2NR^3_2]. The reaction in the presence of an appropriate thiol (R^4SH) lead to the formation of the corresponding unsymmetrical beta- (N,N-dialkylamino) dithioacetals [(PhS) (R^4S) CHR^1CHR^2NR^3_2].Tretment of the (diisopropylamino) magnesium reagent with enemines, derived from various ketones and aldehydes, prior to the interaction with sulfoxides bearing alpha-hydrogens gave the corresponding alpha- (alpha-alkylthio) alkylated ketones and aldehydes. Less

发现仅在α-位置（RSOCH_2R^1）上含有氢的亚硫氧化物与四甲基磷酸二哌替尼组试剂反应，该试剂是通过与乙基二酰胺的2,2,6,6,6-四甲基甲基二酰胺中的2,2,6,6,6-四甲基甲基二酰胺相对应育二二苯基乙酸硫酸乙烯二氢酸酯酸酯的相对生成的，这是在原位产生的。 （rschr^1sr）。在α-位和β-位置（rsochr^1chr^2r^3）上使用氢含亚硫氧化物的硫氧化物与镁酰胺的处理可提供相应的乙烯基硫化物（RSCR^1 = Cr^2r^3）。阐明了导致产物的途径涉及形成硫稳定的碳离子中间体的形成，并将这些反应扩展到一系列有机硫化合物的合成。 The reaction of sulfoxides bearing alpha-hydrogen (s) (RSOCHR^1R^2) With the diisopropylaminomagnesium reagent, which was generated in situ by the treatment of diisopropylamine with an excess … More amount of appropriate Grignard reagents (R^3MgBr), resulted in the formation of the corresponding sulfides (RSCR^1R^2R^3).可以获得高达75％E.E.的光学活性硫化物。通过使用光学活性的硫氧化物或继发胺。（二异丙基氨基）镁试剂（由二异丙胺和溴化乙基溴化物产生，在与硫化固醇（r^1so）的硫化液（r^1so）之前，用硫醇（r^4SH）用硫醇（r^4SH）处理（r^4SH） （r^1scr^2r^4）。用（dialkylamino）镁试剂的乙烯基亚砜（Phsochr^1 = Chr^2）处理，该试剂是由次生胺（R^3_2NH）和乙基镁溴化的，被证明是beta-beta-beta-beta-beta-dial-dial-dial-dial-dial-dialamino [phio）[ _2chr^1chr^2nr^3_2]。在存在适当的硫醇（r^4SH）的情况下的反应导致形成相应的不对称β-（n，n，n-dialkylamino）dithioEcetals [（phs）（r^4S）chr^1chr^1chr^2nr^3_2]。在与含有α-氢元的硫氧化物相互作用之前，（二异丙基氨基）镁试剂与源自各种酮和醛的敌人，从而获得了相应的α-（α-烷基硫硫代）烷基化的酮基因酮和醛。较少的

项目成果

小林和裕: "Reductive α-Substitution of Sulfoxides with Grignard Reagents Promoted by a Magnesium Amide" Bulletin of the Chemical Society of Japan. 69. 441-443 (1996)

Kazuhiro Kobayashi：“氨基镁促进的格氏试剂对亚砜的还原性 α-取代”日本化学会通报 69. 441-443 (1996)。

Kazuhiro Kobayashi: "Reductive alpha-Substitution of Sulfoxides with Grignard Reagents Promoted by a Magnesium Amide" Bulletin of the Chemical Society of Japan. 69. 441-443 (1996)

Kazuhiro Kobayashi：“氨基镁促进的格氏试剂对亚砜的还原性 α 取代”日本化学会通报。

小林 和裕: "An Efficient Synthesis of Unsymmetrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of the Chemical Society of Japan. 69・9. 2645-2647 (1996)

Kazuhiro Kobayashi：“通过氨基镁诱导的普默勒型反应，从亚砜和硫醇中有效合成不对称二硫缩醛”，日本化学会通报 69・9（1996 年）。

Kazuhiro Kobayashi: "An Efficient Synthesis of Unsymmetrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of the Chemical Society of Japan. 69. 2645-2647 (1996)

Kazuhiro Kobayashi：“通过氨基镁诱导的普默勒型反应，从亚砜和硫醇中高效合成不对称二硫缩醛”，日本化学会通报。

小林和裕: "An Efficient Synthesis of Unsymmertrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of Chemical Society of Japan. 69. 2645-2647 (1996)

Kazuhiro Kobayashi：“通过氨基镁诱导的普默勒型反应从亚砜和硫醇中高效合成非对称二硫缩醛”日本化学会通报 69. 2645-2647 (1996)。