贝克-文卡塔拉曼重排反应
贝克-文卡塔拉曼重排反应(Baker-Venkataraman重排)是2-乙酰氧基苯乙酮衍生物在碱作为催化剂之下生成1,3-二酮的反应。这个反应常用于制造色酮和黄酮类化合物。[1][2][3][4][5][6][7][8]反应名称来源于化学家W. Baker和Krishnaswamy Venkataraman。[9][10]
![Baker-Venkataraman重排](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/e/e5/Baker-Venkataraman_Rearrangement_Scheme.png/400px-Baker-Venkataraman_Rearrangement_Scheme.png)
反应机理
在碱作为催化剂的情况之下,首先苯乙酮的羰基α-氢原子被去质子化,形成烯醇负离子。接着烯醇负离子以碳端亲核进攻苯酚酯的碳原子,形成环状的氧负离子。之后氧负把酚氧挤出去,酰基转移到苯乙酮一端,反应后酸化得二酮产物。
![Baker-Venkataraman反应机理](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/e/e0/Baker-Venkataraman-Umlagerung_Mechanismus.svg/600px-Baker-Venkataraman-Umlagerung_Mechanismus.svg.png)
参见
参考文献
- ^ T. S. Wheeler. Flavone. Organic Syntheses. 1952, 32: 72 [2009-05-27]. (原始内容存档于2013-10-12). (also in the Collective Volume (1963) 4:478 (PDF) (页面存档备份,存于互联网档案馆)).
- ^ Jain, P. K.; et al.. A Facile Baker-Venkataraman Synthesis of Flavones using Phase Transfer Catalysis. Synthesis. 1982, 1982: 221–222. doi:10.1055/s-1982-29755.
- ^ Kalinin, A. V.;Da Silva, A. J. M.;Lopes, C. C.;Lopes, R. S. C.;Snieckus, V. Directed ortho metalation - cross coupling links. Carbamoyl rendition of the baker-venkataraman rearrangement. Regiospecific route to substituted 4-hydroxycoumarins. Tetrahedron Lett. 9 July 1998, 39 (28): 4995–4998. doi:10.1016/S0040-4039(98)00977-0.
- ^ Kraus, G. A.; Fulton, B. S. Wood, S.H.J.Org.Chem. 1984, 49, 3212
- ^ Reddy, B.P.; Krupadanam, G.L.D.J. Heterocycl. Chem 1996, 33, 1561
- ^ Kalinin, A.V.; Sneckus, V. Tetrahedron Lett. 1998, 39 4999
- ^ Thasana, N.; Ruchirawat, S. Tetrahedron Lett. 2002, 43, 4515
- ^ Santo, C.M.M.;Sliva, A.M.S. Cavaleiro, J. A.S. Eur.J. Org. Chem. 2003, 4575
- ^ Baker, W. Molecular rearrangement of some o-acyloxyacetophenones and the mechanism of the production of 3-acylchromones. J. Chem. Soc. 1933: 1381–1389. doi:10.1039/JR9330001381.
- ^ Mahal, H. S.; Venkataraman, K. Synthetical experiments in the chromone. group. XIV. Action of sodamide on 1-acyloxy-2-acetonaphthones. J. Chem. Soc. 1934: 1767–1769. doi:10.1039/JR9340001767.
外部链接
- Baker-Venkataraman重排反应 (页面存档备份,存于互联网档案馆)于organic-chemistry.org(英文)