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Danheiser成環反應

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Danheiser成環反應(Danheiser annulation),又稱Danheiser TMS-環戊烯成環反應(Danheiser TMS-Cyclopentene annulation)[1][2][3][4][5][6]

α,β-不飽和與三烴基硅基(如三甲基硅基三異丙基硅基丙二烯路易斯酸存在下發生反應,生成三烴基硅基環戊烯


Danheiser成環反應
Danheiser成環反應


α,β-不飽和太活潑,反應會生成大量副產物;而α,β-不飽和則太不活潑,反應速度慢,產率低;環狀和開鏈的酮都可以用作反應底物。這個反應是同面英語Antarafacial and suprafacial反應,具有高度立體選擇性。

反應機理

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路易斯酸四氯化鈦首先活化α,β-不飽和酮的羰基,得到烯丙位碳正離子中間體,然後被三烴基硅基丙二烯進攻得到乙烯基碳正離子英語vinyl cation中間體A;臨近的硅原子可以穩定乙烯基碳正離子(中間體B),或者可以發生1,2-重排反應得到中間體C;接下來鈦烯醇化物進攻中間體C的碳正離子就可以得到環戊烯。有時中間體A也會生成副產物DF

Danheiser成環反應機理
Danheiser成環反應機理

參見

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參考資料

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  1. ^ "TMS-Cyclopentene Annulation: A Regiocontrolled Approach to the Synthesis of Five-Membered Rings", R. L. Danheiser, D. J. Carini, and A. Basak, J. Am. Chem. Soc. 1981, 103, 1604.
  2. ^ "Scope and Stereochemical Course of the (Trimethylsilyl)cyclopentene Annulation", R. L. Danheiser, D. J. Carini, D. M. Fink, and A. Basak, Tetrahedron 1983, 39, 935.
  3. ^ "The Reaction of Allenysilanes with α,β-Unsaturated Acylsilanes: New Annulation Approaches to Five and Six-Membered Carbocyclic Compounds", R. L. Danheiser and D. M. Fink, Tetrahedron Lett. 1985, 26, 2513.
  4. ^ "A General [3+2] Annulation: cis-4-Exo-isopropenyl-1,9-dimethyl-8-(trimethylsilyl)bicyclo-[4.3.0]non-8-en-2-one", R. L. Danheiser, D. M. Fink, and Y. -M. Tsai, Organic Syntheses 1988, 66, 8.
  5. ^ "Organic Syntheses Based on Name Reactions", By Alfred Hassner and C. Stumer, Elsevier, p. 78, 2002
  6. ^ "Name Reactions: A Collection of Detailed Reaction Mechanisms", By Jie Jack Li, Springer, p. 102, 2003