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

基本信息

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

项目摘要

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

结果发现，仅在α位带有氢的亚砜（RSOCH_2R^1）与四甲基哌啶镁试剂反应，该试剂是通过在回流乙醚中用乙基溴化镁处理2,2,6,6-四甲基哌啶在原位生成的。室温下生成相应的二硫缩醛(RSCHR^1SR)。发现在α-位和β-位上均带有氢的亚砜(RSOCHR^1CHR^2R^3)与酰胺镁一起产生相应的乙烯基硫醚(RSCR^1=CR^2R^3)并伴随相应的二硫缩醛途径。阐明了硫稳定碳正离子中间体的形成，并将这些反应扩展到一系列有机硫的合成带有α-氢的亚砜(RSOCHR^1R^2)与二异丙氨基镁试剂的反应，该试剂是通过用过量的格氏试剂(R^3MgBr)处理二异丙胺而原位生成的，导致形成相应的硫化物（RSCR^1R^2R^3），最多可以获得光学活性的硫化物。 75% e.e. 通过使用光学活性亚砜或仲胺。由二异丙胺和乙基溴化镁生成的（二异丙氨基）镁试剂在与 α- 处带有氢的亚砜相互作用之前，用硫醇 (R^4SH) 进行处理位置 (R^1SOCHR^2R^3) 提供不对称的二硫缩醛(R^1SCR^2R^3SR^4)。用由仲胺 (R^3_2NH) 和乙基溴化镁生成的（二烷基氨基）镁试剂处理乙烯基亚砜 (PhSOCHR^1=CHR^2)，结果证明得到不对称β-(N,N-二烷基氨基)二硫缩醛[(PhS) _2CHR^1CHR^2NR^3_2] 在适当的硫醇 (R^4SH) 存在下发生反应，导致形成相应的不对称 β-(N,N-二烷基氨基) 二硫缩醛 [(PhS) (R^4S)。 CHR^1CHR^2NR^3_2]。用烯胺处理（二异丙氨基）镁试剂，衍生自各种酮和醛，在与带有α-氢的亚砜相互作用之前产生相应的α-(α-烷硫基)烷基化酮和醛。