Substrate-directed hydroacylation: rhodium-catalyzed coupling of vinylphenols and nonchelating aldehydes.
We report a protocol for the hydroacylation of vinylphenols with aryl, alkenyl, and alkyl aldehydes to form branched products with high selectivity. This cross-coupling yields α-aryl ketones that can be cyclized to benzofurans, and it enables access to eupomatenoid natural products in four steps or less from eugenol. Excellent reactivity and high levels of regioselectivity for the formation of the branched products were observed. We propose that aldehyde decarbonylation is avoided by the use of an anionic directing group on the alkene and a diphosphine ligand with a small bite angle.
Department of Chemistry, University of California, Irvine, CA 92697-2025 (USA); Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 (Canada).
Stephen K
SK
Murphy
Achim
A
Bruch
Vy M
VM
Dong
D000215:Acylation; D000447:Aldehydes / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000737:chemistry; D010636:Phenols / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D001572:Benzofurans; D007659:Ketones; D010636:Phenols; D012238:Rhodium
CH activation; benzofurans; hydroacylation; regioselectivity; rhodium catalysis