Chiral Brønsted Acid-Catalyzed Allylboration of Aldehydes

• Published in: Journal of the American Chemical Society Vol. 132; no. 34; pp. 11884 - 11886
• Main Authors: Jain, Pankaj, Antilla, Jon C
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.09.2010; Amer Chemical Soc
• Subjects: Alcohols - chemical synthesis; Alcohols - chemistry; Aldehydes - chemistry; Boronic Acids - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Molecular Structure; Organophosphonates - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; ASYMMETRIC ALLYLBORATION; REAGENTS; DIASTEREOSELECTIVE SYNTHESIS; PHOSPHORIC-ACID; HOMOALLYLIC ALCOHOLS; COMPLEXES; CARBONYL-COMPOUNDS; ENANTIOSELECTIVE ALLYLATION; LEWIS-ACIDS; CROTYLBORATION
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja104956s

The catalytic enantioselective allylation of aldehydes is a long-standing problem of considerable interest to the chemical community. We disclose a new high-yielding and highly enantioselective chiral Brønsted acid-catalyzed allylboration of aldehydes. The reaction is shown to be highly general, with a broad substrate scope that covers aryl, heteroaryl, α,β-unsaturated, and aliphatic aldehydes. The reaction conditions are also shown to be effective for the catalytic enantioselective crotylation of aldehydes. We believe that the high reactivity of the allylboronate is due to protonation of the boronate oxygen by the chiral phosphoric acid catalyst.