A new photoa ldol route to α-amino-β-hydroxy carboxylic acid esters is initiated by the photocycloaddition of aromatic or aliphatic aldehydes to 5-methoxyoxazoles. The 4- unsubstituted 5-methyloxazole 1 gave the cycloadducts 8a-f in high yields and excellent exo- diastereoselectivities. Hydrolysis of 8a-f gives the N-acetyl α-amino-β-hydroxy esters 9a-f, which could be subsequently converted into the corresponding Z-didehydro α-amino ...