Hauser-Kraus环化反应会

水溶液条件下，氟酞类氟化和α，β-不饱和负离子氟化立体选择性关环得到氟并氢醌的重排。加入氟化银氟化氢醌可以化学合成氟醌。

重排机理

重排实例

Hydroquinone (4). To LDA (3.3 mmol) in THF (4 mL) and HMPA at -78 ℃ was added 3-cyanophthalide 1 (3 mmol) in THF (3 mL) over 2 min. After 10 min stirring at -78 ℃, 2 (3 mmol) in THF (3 mL) was added over 1 min. After warming to 0 ℃, the mixture was quenched with AcOH and diluted with Et2O and water. Workup and chromatography yielded pure hydroquinone 4.

【 Tet Lett. , 1978, 19, 2263】

Quinone (11). To a stirred solution of tBuOLi (9.84 mmol) in THF (40 mL) at -60 ℃ was added a solution of phthalide 9 (3.28 mmol) in THF (5 mL) under N2. After stirring the yellowish solution at -60 ℃ for 25 min, 10 (1.5 eq) in THF (5 mL) was added and stirring continued for 1 h at the same temp and further 2–6 h at r.t. Usual workup and chromatography or recrystallization afforded 11 in 66%

yield.

【 J Org Chem. , 2007, 72, 4981】

【 Australian Journal of Chemistry , 2003, 56, 691-702】

【 Synlett , 2007, 741-744】

系统性典籍

1 Hauser FM J Am Chem Soc 1977 99 4533

2 Hauser FM J Org Chem 1978 43 178,180

3 Kraus GA Tet Lett 1978 19 2263

4 David YB Tet Lett 1983 24 3533

5 Mal D Tet Lett 2006 47 1071

6R Mal D Chem Rev 2007 107 1892

7 Mal D J Org Chem 2007 72 4981

8 Nicolaou KC J Am Chem Soc 2009 131 14812

9 Mal D Org Lett 2009 11 4398

10 Rastroem O Tet Lett 2010 51 75

11 Yu B J Am Chem Soc 2011 133 12433

12 Mal D J Org Chem 2011 76 3392

13 Sulikowski GA Org Lett 2011 13 4538

参考典籍

一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, 207-208

二、APP: ReactionFlash