Total syntheses of isodomoic acids G and H.
The total syntheses of marine natural products belonging to the kainoid family, isodomoic acids G and H, are described. The strategic connection involves a sequential silylcarbocyclization/silicon-based cross-coupling process. These total syntheses were achieved efficiently via a 12- and a 13-step, longest-linear sequence, respectively. The key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of an (l)-vinylglycine-derived 1,6-enyne, a desilylative iodination reaction, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction. The mechanistic insight garnered during the investigation of the iododesilylation reaction enabled stereocontrolled introduction of the iodine with either inversion or retention of double bond configuration. The invertive desilylative iodination leads to the total synthesis of isodomoic acid H, while its congener, isodomoic acid G, was obtained via a retentive iododesilylation.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA. sdenmark@illinois.edu
Liu
Jack Hung-Chang
JH
Muhuhi
Joseck M
JM
D006538:Heptanoic Acids / Q000138:chemical synthesis*; D008387:Marine Toxins / Q000138:chemical synthesis*; D000461:Rhodophyta / Q000737:chemistry
D006538:Heptanoic Acids; D008387:Marine Toxins