Rhodium-Catalyzed Asymmetric Hydroformylation of N-Allyl Amides

Significance

Asymmetric hydroformylation (AHF) is an atom-efficient method for synthesizing enantiomerically pure aldehydes, which are important intermediates for pharmaceuticals and fine chemicals. The substrates for the rhodium-catalyzed AHF are usually limited to simple terminal olefins without α-hydrogens, such as styrene derivatives and vinyl carboxylates. Allylic substrates are particularly challenging because of the potential migration of the double bond, and linear products are obtained in most cases. The authors report an asymmetric rhodium yanphos (L) catalyzed hydroformylation of N-allyl amides and N-allyl sulfon­amides 1. Good branch/linear (b/l) ratios, excellent ee values and conversions were obtained. The products, chiral β^²-amino aldehydes, are useful building blocks in natural product synthesis.