α-Aminomethyl alkyl ketones reacted smoothly with α,β-unsaturated aldehydes via a tandem process catalysed by diphenylprolinol silyl ether/4-bromobenzoic acid. 2-Alkanoyl-3-aryl-5-hydroxy pyrrolidines were prepared in high yields (up to 99%) and enatioselectivities (>99% ee). The absolute configurations of the products were unambiguously confirmed by single-crystal diffraction.