Two concise strategies to synthesize oxazolidin-2-imines by cascade nucleophilic attack/addition cyclization reactions of (Z)-2-bromo-3-phenylprop-2-en-1-ols/3-phenylprop-2-yn-1-ols and diphenyl carbodiimides without a transition-metal catalyst have been developed. The reactions exhibited good substrate applicability tolerance, and a variety of substituted (Z)-4-((Z)-benzylidene)-N,3-diphenyloxazolidin-2-imines were synthesized in moderate to excellent yields with good stereoselectivity. The reports also provided a convenient strategy to synthesize 3-phenylprop-2-yn-1-ols by (Z)-2-bromo-3-phenylprop-2-en-1-ols. The economic and practical methods provide a great advantage for potential industrial synthesis of oxazolidin-2-imines.