Finally, we demonstrated the synthetic potential of ethyl glyoxylate-derived 1aj as a useful denitrogenative ester transfer agent through the post-functionalization of compounds 57 and 58 on a 5 mmol scale (Figure ). Given the high relevance of therapeutic peptides containing -amino acids, we showcase the straightforward preparation of dipeptide 69 through a four step sequence, starting from abundant and cheap precursors. Additionally, important motifs in medicinal chemistry, such as -lactam 71, can be prepared through deprotection of 58 and subsequent Mukaiyama reagent-induced cyclization. In summary, we describe herein an efficient protocol to forge C(sp 3 )-C(sp 3 ) bonds from easily accessible N-sulfonyl hydrazones and C(sp 3 )-H donors via a two-step synthetic strategy, comprising a photocatalytic Hydrogen Atom Transfer and a subsequent fragmentation reaction.