Journal of Organic Chemistry 2009-05-01

Regioselective syntheses of 2- and 4-formylpyrido[2,1-b]benzoxazoles.

Ke-Lai Li, Zong-Bo Du, Can-Cheng Guo, Qing-Yun Chen

Index: J. Org. Chem. 74(9) , 3286-92, (2009)

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Abstract

o-Acetaminophenols (2) reacted with Vilsmeier reagent under Meth-Cohn conditions to yield 2-formylpyrido[2,1-b]benzoxazoles (5) unexpectedly besides the known compounds 2-(benzoxazol-2'-yl)-3-dimethylaminoacroleins (4). Refluxing 4 in acetic anhydride gave 4-formylpyrido[2,1-b]benzoxazoles (6), an isomer of 5. Both 5a and 6a were structurally characterized by X-ray crystallography. A mechanism for the formation of 5 involving sequential chlorination, dimerization, intramolecular elimination of HCl to form the oxazole ring, formylation twice, and regioselective intramolecular nucleophilic cyclization to construct the pyridone ring is proposed.