The BakerâVenkataraman rearrangement is often used in the synthesis of
chromones and
flavones.[3][4][5][6][7][8][9][10] After the base-catalyzed rearrangement, treatment with acid generally affords the chromone or flavone core, though other milder methods have been reported.[11]
Mechanism
A base abstracts the hydrogen atom alpha to the aromatic
ketone, forming an enolate. Then, the enolate attacks the ester carbonyl to form a cyclic
alkoxide. The cyclic intermediate is opened up to form a more stable
phenolate, which is protonated during acidic work-up to give the desired product.
To complete the construction of the chromone or flavone core, cyclodehydration is required. This was commonly afforded by treatment with strong acid, however many milder conditions have now been developed. One proposed mechanism for this dehydration is as follows:
^Baker, W. (1933). "Molecular rearrangement of some o-acyloxyacetophenones and the mechanism of the production of 3-acylchromones". J. Chem. Soc.: 1381â1389.
doi:
10.1039/JR9330001381.
^Mahal, H. S.; Venkataraman, K. (1934). "Synthetical experiments in the chromone. group. XIV. Action of sodamide on 1-acyloxy-2-acetonaphthones". J. Chem. Soc.: 1767â1769.
doi:
10.1039/JR9340001767.
^Jain, P. K.; Makrandi, J. K. (1982). "A Facile Baker-Venkataraman Synthesis of Flavones using Phase Transfer Catalysis". Synthesis. 1982 (3): 221â222.
doi:
10.1055/s-1982-29755.
^Kalinin, A. V.; Da Silva, A. J. M.; Lopes, C. C.; Lopes, R. S. C.; Snieckus, V. (1998). "Directed ortho metalation â cross coupling links. Carbamoyl rendition of the Baker-Venkataraman rearrangement. Regiospecific route to substituted 4-hydroxycoumarins". Tetrahedron Letters. 39 (28): 4995â4998.
doi:
10.1016/S0040-4039(98)00977-0.
^Reddy, B.P.; Krupadanam, G.L.D. (1996). "The synthesis of 8-allyl-2-styrylchromones by the modified baker-venkataraman transformation". J. Heterocycl. Chem. 33 (6): 1561.
doi:
10.1002/jhet.5570330602.
^Kalinin, A.V.; Sneckus, V. (1998). "4,6-Dimethoxy-3,7-dimethylcoumarin from Colchicum decaisnei. Total synthesis by carbamoyl Baker-Venkataraman rearrangement and structural revision to isoeugenetin methyl ether". Tetrahedron Lett. 39 (28): 4999.
doi:
10.1016/S0040-4039(98)00978-2.
^Thasana, N.; Ruchirawat, S. (2002). "The application of the BakerâVenkataraman rearrangement to the synthesis of benz[b]indeno[2,1-e]pyran-10,11-dione". Tetrahedron Lett. 43 (25): 4515.
doi:
10.1016/S0040-4039(02)00818-3.
^Santos, C.M.M.; Silva, A.M.S.; Cavaleiro, J.A.S. (2003). "Synthesis of New Hydroxy-2-styrylchromones". Eur. J. Org. Chem. 2003 (23): 4575.
doi:
10.1002/ejoc.200300468.
hdl:10198/3932.
^Santos, Clementina M.; Silva, Artur M. S. (2017). "An Overview of 2-Styrylchromones: Natural Occurrence,Synthesis, Reactivity and Biological Properties". Eur. J. Org. Chem. 2017 (22): 3115â3133.
doi:
10.1002/ejoc.201700003.
hdl:10198/14517 – via Reaxys.