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硫叶立德

硫葉立德,又名硫鎓内鹽,是葉立德的一種。其中帶負電荷,與其相鄰的帶正電荷,因此是兩性離子的一種[1]。跟其他葉立德一樣,硫葉立德在有機合成中有很多應用[2]

硫葉立德有以下共振式[3]

硫葉立德有不同種類,如下:

它最早於1961年由William Johnson發現[4]

合成

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烷亞甲基型硫葉立德可以有二甲硫醚碘甲烷反應成鹽,再與强鹼(如氫化鈉等)反應製備而成[5]

而亞碸型葉立德(又名氧硫葉立德)可以由二甲亞碸碘甲烷,再經過氨基鈉處理製備而成[6]

硫葉立德非常不穩定,一般在反應中原位製備並進行反應[7][8]

反應

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硫葉立德可以與α,β-不飽和羰基化合物亞胺等含有雙鍵有機化合物發生約翰遜–科里–柴可夫斯基反應,生成環丙烷環氧化合物氮雜環丙烷等三元環。反應式如下:

Johnson–Corey–Chaykovsky Reaction
Johnson–Corey–Chaykovsky Reaction

反應機理如下:

Mechanism of the Johnson–Corey–Chaykovsky reaction
Mechanism of the Johnson–Corey–Chaykovsky reaction

反應首先是硫葉立德對底物(羰基亞胺基團等)的親核加成,然後發生分子内的親核取代反應形成三元環,鋶正離子離去,形成產物[6]

重要性

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硫葉立德是一種非常有用的有機試劑,很多個全合成都使用了它[9][10][11][12][13]

其中,硫葉立德的約翰遜–科里–柴可夫斯基反應提供了一條由醛、酮爲原料有效合成環氧化合物的途徑。

參見

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參考資料

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  1. ^ Illustrated Glossary of Organic Chemistry. 加利福尼亞大學洛杉磯分校. [2021-07-27]. (原始内容存档于2021-07-27) (英语). 
  2. ^ McMurry, John. Organic Chemistry, 7th Ed.. Thomson Brooks/Cole. 2008: 720–722. ISBN 978-0-495-11258-7. 
  3. ^ Samer Gnaim. Sulfur Ylide Chemistry (PDF). 08/01/20 [2021-07-27]. (原始内容存档 (PDF)于2021-08-19) (英语). 
  4. ^ A. William Johnson, Robert B. LaCount. The Chemistry of Ylids. VI. Dimethylsulfonium Fluorenylide-A Synthesis of Epoxides. J. Am. Chem. Soc. 1961, 83 (2): 417–423 [2021-07-27]. doi:10.1021/ja01463a040. (原始内容存档于2021-07-27). 
  5. ^ Corey, E. J.; Chaykovsky, M. METHYLENECYCLOHEXANE OXIDE. Organic Syntheses. 1969, 49: 78 [2009-10-17]. (原始内容存档于2010-03-31). 
  6. ^ 6.0 6.1 邢其毅; 裴堅; 裴偉偉; 徐瑞秋. 基礎有機化學.硫葉立德的反應 第四版. : p.647 [2021-07-27]. ISBN 9787301272121. 
  7. ^ E. J. Corey, Michael Chaykovsky. Dimethylsulfoxonium Methylide. J. Am. Chem. Soc. 1962, 84 (5): 867–868. doi:10.1021/ja00864a040. 
  8. ^ E. J. Corey, Michael Chaykovsky. Dimethyloxosulfonium Methylide ((CH3)2SOCH2) and Dimethylsulfonium Methylide ((CH3)2SCH2). Formation and Application to Organic Synthesis. J. Am. Chem. Soc. 1965, 87 (6): 1353–1364. doi:10.1021/ja01084a034. 
  9. ^ Aggarwal, V. K.; Richardson, J. The complexity of catalysis: origins of enantio- and diastereocontrol in sulfur ylide mediated epoxidation reactions. Chemical Communications. 2003: 2644. doi:10.1039/b304625g. 
  10. ^ Aggarwal, V. K.; Winn, C. L., Catalytic, Asymmetric Sulfur Ylide-Mediated Epoxidation of Carbonyl Compounds: Scope, Selectivity, and Applications in Synthesis, Accounts of Chemical Research, 2004, 37: 611, doi:10.1021/ar030045f 
  11. ^ Gololobov, Y. G.; Nesmeyanov, A. N.; lysenko, V. P.; Boldeskul, I. E., Twenty-five years of dimethylsulfoxonium ethylide (corey's reagent), Tetrahedron, 1987, 43: 2609, doi:10.1016/s0040-4020(01)86869-1 
  12. ^ Li, A.-H.; Dai, L.-X.; Aggarwal, V. K., Asymmetric Ylide Reactions: Epoxidation, Cyclopropanation, Aziridination, Olefination, and Rearrangement, Chemical Reviews, 1997, 97: 2341, doi:10.1021/cr960411r 
  13. ^ McGarrigle, E. M.; Myers, E. L.; Illa, O.; Shaw, M. A.; Riches, S. L.; Aggarwal, V. K., Chalcogenides as Organocatalysts, Chemical Reviews, 2007, 107 (12): 5841 [2021-07-27], doi:10.1021/cr068402y, (原始内容存档于2021-07-27) 
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硫叶立德
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