Benzilic acid rearrangement（二苯基乙醇酸重排）

苯偶酰在碱性条件下，通过芳基迁移生成二苯基乙醇酸的反应。脂肪族α-二酮虽然也能进行同样的反应，环状的α-二酮的话，会生成环缩小产物。

反应机理

醇负离子脱掉羧酸H形成二苯基乙醇酸负离子是此反应进行的主要驱动力。

反应实例

【Tetrahedron 1963, 19, 1037-1049】

【Synthesis 2006, 15, 2556-2562】

【Angew. Chem. Int. Ed. 2008, 47, 5082-5084】

【Beilstein J. Org. Chem. 2013, 9, 594–601】

相关文献

1. Liebig, J. Justus Liebigs Ann. Chem. 1838, 27. Justus von Liebig (1803-1873) pursued his Ph.D. in organic chemistry in Paris under the tutelage of Joseph Louis Gay-Lussac (1778-1850). He was appointed the Chair of Chemistry at Giessen University, which incited a furious jealousy amongst several of the professors already working there because he was so young. Fortunately, time would prove the choice was a wise one for the department. Liebig would soon transform Giessen from a sleepy university to a mecca of organic chemistry in Europe. Liebig is now considered the father of organic chemistry. Many classic name reactions were published in the journal that still bears his name, Justus Liebigs Annalen der Chemie.2

2. Zinin, N. Justus Liebigs Ann. Chem. 1839, 31, 329.

3. Georgian, V.; Kundu, N. Tetrahedron 1963, 19, 1037-1049.

4. Robinson, J. M.; Flynn, E. T.; McMahan, T. L.; Simpson, S. L.; Trisler, J. C.; Conn, K. B. J. Org. Chem. 1991, 56, 6709-6712.

5. Fohlisch, B.; Radl, A.; Schwetzler-Raschke, R.; Henkel, S. Eur. J. Org. Chem. 2001, 4357-4365.

6. Patra, A.; Ghorai, S. K.; De, S. R.; Mal, D. Synthesis 2006, 15, 2556-2562.

7. Selig, P.; Bach, T. Angew. Chem. Int. Ed. 2008, 47, 5082-5084.

8. Kumar, R. R.; Balasubramanian, M. Benzilic Acid Rearrangement. In Name Reactions for Homologations-Part II; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 395-405.(Review).

9. Sultana, N.; Fabian, W. M. F. Beilstein J. Org. Chem. 2013, 9, 594–601.

尤斯图斯·冯·李比希 (1803-1873)在约瑟夫·路易·盖-吕萨克 (1778-1850)的指导下在巴黎获得有机化学方面的Ph.D.学位。在德国吉森大学大学任教，但由于他他年轻招致了很多已在职同事的嫉妒。但时间很快就证明学校的选择是明智的，他很快就将本来在有机化学方面寂寂无闻的吉森大学变为全欧知名大学。现在李比希被尊为有机化学之父。许多期刊上发表的经典人名反应都以他的名字命名，如期刊也以他命名（ Justus Liebigs Annalen der Chemie）。

编译自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Benzilic acid rearrangement，page 44-45.