Photolysis of optically active chromium aminocarbene complex (R)-1 in the presence of functionalized, unprotected alpha-amino acid esters of serine, cysteine, methionine, and tyrosine led to the production of dipeptides in good yield without competitive coupling at the side chain functional groups. The diesters of aspartic and glutamic acid also coupled efficiently. Even sterically hindered alpha,alpha-disubstituted alpha-amino acids and N-methyl- and N-methyl-alpha,alpha-dialkyl-alpha-amino acids coupled efficiently to the photogenerated amino acid residue precursor, allowing introduction of these normally difficult-to-couple hindered amino acids into peptides.