Studies on Characteristic Reactions in the Chalcogeno -Baylis -Hillman Reactions

硫属元素-Baylis-Hillman反应中特征反应的研究

• 批准号: 12672056
• 负责人: KATAOKA Tadashi
• 金额: $ 2.18万
• 依托单位: Gifu Pharmaceutical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12672056/
• 关键词: Baylis-Hillman reaction; sulfide; Lewis acid; Michael reaction; aldol reaction; halomethylene aldol; alkyne; β-haloacrylic acid ester

In order to overcome the drawback of the Baylis-Hillman reaction, "the slow rate," we developed the chalcogemde-TiCl_4-mediated tandem Michael-aldol reactions. The reactions had been deemed to be a chalcogene version of the Baylis-Hillman reaction, because the Baylis-Hillman adducts were given after purification of the products by the preparative TLC on silica gel. However, the initial products were α-chloromethyl aldols and were dehydrochlorinated during purification by the preparative TLC. The reactions of S-ethyl thioacrylate and keto esters gave much better results than the Baylis-Hillman reactions of ten. The reactions of acetylenic ketones and esters produced α-chloromethylene aldols. The chalcogenides were necessary for the reactions of α,β-unsaturated esters. The reactions of acetylenic ketones and esters and α-keto esters did not occur when tertiary amines were used as a catalyst instead of a Chalcogenide and TiCl_4.We next studied the reaction in which a chalcogenide worked as Lewis base and found that sulfanyl substituent intramolecularly added to an enone to form a cychc sulfomum betaine. The tandem Michael-aldol reactions of 1- [2-(methylsulfanyDphenyl]prop-2-en-1-one or the seleno congener with aldehydes in the presence of BF_3・E_2O gave the Baylis-Hillman adduct and onium salt, and 3-(α-hydroxybenzyl) selenochromanone from the seleno congener.

为了克服Baylis-Hillman反应速度慢的缺点，我们开发了氯化钛介导的串联Michael-aldol反应。这些反应被认为是一个硫原版的Baylis-Hillman反应，因为Baylis-Hillman加合物是在硅胶制备层析纯化产物后得到的。但初始产物为α-氯甲基醛，在制备层析纯化过程中被脱氢氯化。硫代丙烯酸s-乙酯与酮酯的反应比贝里斯-希尔曼反应的效果好得多。乙炔酮与酯反应生成α-氯甲基醛。硫族化合物是α，β-不饱和酯反应所必需的。叔胺代替硫系化合物和TiCl_4催化剂时，不发生乙炔酮酯和α-酮酯的反应。接下来，我们研究了硫族化合物作为刘易斯碱的反应，发现在分子内，磺胺基取代基加入到烯酮上，形成环磺胺甜菜碱。在BF_3·E_2O的存在下，1-[2-（甲基磺酰二苯基）2-烯-1- 1或硒同族物与醛的串联Michael-aldol反应得到bayls - hillman加合物和铵盐，并从硒同族物中得到3-（α-羟基苄基）硒代romanone。

项目成果

T.Kataoka,T.Iwama,H.Kinoshita,T.Iwamura,S.Watanabe: "Chalcogenide-TiCl_4-mediated Reactions of S-Ethyl Thioacrylate with Aldehydes"J.Organomet.Chem.. 611. 455-462 (2000)

T.Kataoka,T.Iwama,H.Kinoshita,T.Iwamura,S.Watanabe：“硫族化合物-TiCl_4介导的S-硫代丙烯酸乙酯与醛的反应”J.Organomet.Chem.. 611. 455-462 (2000)

T. Kataoka, S. Kinoshita, H. Kinoshita, M. Fujita, T. Iwamura, S. Watanabe: "Selfassisted Tandem Michael-aldol Reactions Mechanism of α,β-Unsaturated Ketones with Aldehydes"Chem. Commun.. 1958-1959 (2001)

T. Kataoka、S. Kinoshita、H. Kinoshita、M. Fujita、T. Iwamura、S. Watanabe：“α,β-不饱和酮与醛的自辅助串联迈克尔-醛醇反应机制”化学。 1958-1959 (2001)

T. Iwamura, M. Fujita, T. Kawakita, S. Kinoshita, S. Watanabe, T. Kataoka: "Dimethyl Sulfide-boron tribromide-mediated Reactions of α,β-Unsaturated Ketones with Aldehydes : One-pot Synthesis of Baylis-Hillman Adducts and α-Halomethyl Enones"Tetrahedron. 5

T. Iwamura、M. Fujita、T. Kawakita、S. Kinoshita、S. Watanabe、T. Kataoka：“二甲基硫醚-三溴化硼介导的 α,β-不饱和酮与醛的反应：Baylis-的一锅合成Hillman 加合物和 α-卤甲基烯酮"四面体。5

T.Kataoka, H.Kinoshita, S.Kinoshita, T.Iwamura, S.Watanabe: "A Convenient Synthesis of α-Halomethylene Aldols or β-Halo-α-(hydroxyalkyl)-acrylates Using the Chalcogeno-Baylis-Hillman Reaction"Angew.Chem.Int.Ed.. 39. 2358-2360 (2000)

T.Kataoka、H.Kinoshita、S.Kinoshita、T.Iwamura、S.Watanabe：“利用 Chalcogeno-Baylis-Hillman 反应方便合成 α-卤代亚甲基醛醇或 β-卤代-α-(羟烷基)-丙烯酸酯” Angew.Chem.Int.Ed. 39. 2358-2360 (2000)

T.Kataoka,H.Kinoshita,T.Iwamura,S.Watanabe,G.Tanabe: "Reexamination of Products and the Reaction Mechanism of the Chalcogeno-Baylis-Hillman Reaction"Tetrahedron. 56. 4725-4731 (2000)

T.Kataoka，H.Kinoshita，T.Iwamura，S.Watanabe，G.Tanabe：“硫族-Baylis-Hillman反应的产物和反应机理的重新检验”四面体。