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

研究发现，仅在α位上带有氢的亚砜（RSOCH_2R^1）与四甲基哌啶基镁试剂在室温下反应生成相应的二硫代缩醛（RSCHR^1SR），四甲基哌啶基镁试剂是由2，2，6，6-四甲基哌啶与溴化乙基镁在三乙醚中原位反应生成的。用氨基镁处理α位和β位都带有氢的亚砜（RSOCHR^1CHR^2R^3），可以得到相应的乙烯基硫醚（RSCR^1=CR^2R^3），并伴随相应的二硫代缩醛。研究了含α-氢亚砜（RSOCHR^1R^2）与二异丙基氨基镁试剂的反应，该试剂是由二异丙基胺与过量的二异丙基氨基镁反应原位生成的，反应产物中的α-氢亚砜（RSOCHR^1R^2）与二异丙基氨基镁试剂的反应产物中的α-氢亚砜（RSOCHR^1R^2 ...更多信息 加入适量的格氏试剂（R^3MgBr），生成相应的硫化物（RSCR^1R^2R^3）。在75%e.通过使用光学活性亚砜或仲胺。（二异丙基氨基）镁试剂，由二异丙基胺和乙基溴化镁生成，在与在α-位上带有氢的亚砜相互作用之前，用硫醇（R^4SH）处理（R^1SOCHR^2R^3），得到不对称的二硫代缩醛（R^1SCR^2R^3SR^4）乙烯基亚砜的处理（PhSOCHR^1=CHR^2），由仲胺（R^3_2NH）和乙基溴化镁生成的（二烷基氨基）镁试剂，证明得到不对称的β-（N，N-二烷基氨基）二硫代缩醛[（PhS）_2CHR_1CHR_2NR_3_2]。在适当的硫醇（R^4SH）存在下的反应导致形成相应的不对称β-（N，N-二烷基氨基）二硫代缩醛[（PhS）（R^4S）CHR^1CHR^2NR^3_2]。（二异丙基氨基）镁试剂与衍生自各种酮和醛的烯，在与带有α-氢的亚砜相互作用之前，得到相应的α-（α-烷硫基）烷基化酮和醛。少

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）。

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)。

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。