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The first example of intramolecular nucleophilic addition of 1,4-diazabutatriene to ester is disclosed. This approach provides a facile and versatile synthesis for functionalized 2H-1,4-benzoxazines through a metal-, reagent-, and solvent-free condition. Experimental and computational studies revealed the pivotal role of 1,5-acyl migration as the self-catalytic step in the reaction selectivity.
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