Enantioselective Rh-Catalyzed Anti-Markovnikov Hydroformylationof 1,1-Disubstituted Allylic Alcohols and Amines: An Efficient Routeto Chiral Lactones and Lactams

Rh-catalyzed highly enantioselective anti-Markovnikov hydroformylation of 1,1-disubstituted allylic alcohols and amines has been achieved. By using a chiral hybrid phosphorus ligand, a series of challenging 1,1-disubstituted allylic alcohols and amines were transformed to valuable chiral lactones and lactams with good yields and high enantioselectivities (up to 90% yield and 93% enantiomeric excess (ee)) under very mild reaction conditions (50 °C, CO/H2 = 2.5/2.5 bar). Furthermore, gram-scale reaction and diverse synthetic transformations have also been achieved, demonstrating the wide synthetic utility of this methodology.