Regioselective and Enantioselective Hydroformylation of Dialkylacrylamides

• Published in: Advanced synthesis & catalysis Vol. 352; no. 6; pp. 1047 - 1054
• Main Authors: Noonan, Gary M., Newton, David, Cobley, Christopher J., Suárez, Andrés, Pizzano, Antonio, Clarke, Matthew L.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 19.04.2010; WILEY‐VCH Verlag; Wiley
• Subjects: Acrylic acid; Aldehydes; Amides; asymmetric carbonylation; Asymmetry; Catalysis; Chemistry; Chemistry, Applied; Chemistry, Organic; hydroaminomethylation; hydroformylation; Ligands; Physical Sciences; racemization; Science & Technology; Synthesis; hydroaminomethylation; ASYMMETRIC HYDROFORMYLATION; RH-CATALYSTS; TANDEM REACTION SEQUENCES; COMPLEXES; asymmetric carbonylation; aldehydes; SEQUENTIAL HYDROFORMYLATION; LIGANDS; RHODIUM-CATALYZED HYDROFORMYLATION; SYNTHETIC APPLICATIONS; OLEFINS; METAL; hydroformylation; racemization
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.200900871

Dimethylacrylamide can be hydroformylated with very high chemo‐ and regioselectivity. Asymmetric hydroformylation of this substrate is possible, provided steps are taken to minimise racemisation of the aldehyde products, and this work demonstrates the effect of various conditions and variables on racemisation. Using the Landis diazaphospholane ligands up to 68% ee can be realised under very mild conditions. Other dialkylacrylamides were also hydroformylated under mild conditions giving similar or better enantioselectivities, including the Weinreb amide of acrylic acid (71% ee), and the asymmetric hydroformylation of diethylacrylamide producing the chiral aldehyde with up to 82% ee.