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

• Published in: Journal of organic chemistry 1998-03, Vol.63 (6), p.1863-1871
• Main Authors: Chowdhury, Chinmay, Chaudhuri, Gopeswar, Guha, Subhadra, Mukherjee, Alok k, Kundu, Nitya G
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo9717595

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 (1a) or 2-hydroxy-3-(prop-2-ynyloxy)naphthalene (1b) 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 regio- and stereoselective and also amenable to bisheteroannulation. The Z-stereochemistry of products 3 was established firmly from 1H NMR, 3 J CH 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.