203173-96-0Relevant articles and documents
Palladium-Catalyzed Heteroannulation Leading to Heterocyclic Structures with Two Heteroatoms: A Highly Convenient and Facile Method for a Totally Regio- and Stereoselective Synthesis of (Z)-2,3-Dihydro-2-(ylidene)-1,4-benzo- and -naphtho [2,3-b]dioxins
Chowdhury, Chinmay,Chaudhuri, Gopeswar,Guha, Subhadra,Mukherjee, Alok K.,Kundu, Nitya G.
, p. 1863 - 1871 (1998)
A facile method for the synthesis of (Z)-2,3-dihydro-2-(ylidene)-1,4-benzo- and naphthodioxins (3) has been developed using palladium-copper catalysis. Aryl halides 2 were found to react with mono-prop-2-ynylated catechol (la) or 2-hydroxy-3-(prop-2-ynyloxy)naphthalene (Ib) in the presence of (PPh3)2PdCl2 (3.5 mol %) and CuI (7 mol %) in triethylamine by stirring at room temperature for 20 h followed by heating at 100°C for 16 h to give products 3 in good yields. The method is regioand stereoselective and also amenable to bisheteroannulation. The Z-stereochemistry of products 3 was established firmly from 1H NMR, 3JCH values (between vinylic proton and methylenic carbon of the heterocyclic ring), proton NOE measurements, and finally from X-ray analysis. Based on experimental observations and known palladium chemistry, a mechanism has been proposed to explain the regio- and stereoselective product formation. Some of the products 3 were also converted , to 1,4-benzodioxan derivatives 6 using hydrogenation procedure. A uracil derivative of possible biological interest, possessing a 1,4-benzodioxinyl functionality at the C-5 position, has been synthesized.
