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A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides hasbeendeveloped.TheazaoxyallylcationintermediatesareemployedasC ~O3-atomsynthontobuild oxa-heterocycles via the selectivity of suitable cyclization partners. This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and excellent regioselectivity.