Anion-catalyzed addition of gamma-silylallenyl esters to aldehydes: a new entry into [3.2.1] bicyclic natural products.
A significant improvement in the generality and reactivity of MBH-type reactions is made possible by anion catalysis and a 1,3-Brook rearrangement. In this new reaction, both aliphatic and aromatic aldehydes are rapidly added to silylallenes, leading to gamma-carbinol allenoates at low temperatures. The utility of these reaction products is demonstrated by a fast-tracked synthesis of a [3.2.1] bisoxa bicycle that makes up the framework of many biologically active natural products, including vitisinol D, an antithrombotic agent.
Maity
Pradip
P
Department of Chemistry, Florida Atlantic University, Boca Raton, Florida 33431-0991, USA.
Lepore
Salvatore D
SD
D000447:Aldehydes / Q000737:chemistry*; D000838:Anions; D044946:Biflavonoids / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002392:Catechin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods; D002626:Chemistry, Pharmaceutical / Q000379:methods; D015195:Drug Design; D004952:Esters / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D044945:Proanthocyanidins / Q000737:chemistry; D013379:Substrate Specificity; D013696:Temperature
D000447:Aldehydes; D000838:Anions; D044946:Biflavonoids; D001643:Bridged Bicyclo Compounds; D004952:Esters; D044945:Proanthocyanidins; C479587:vitisinol; C542349:vitisinol D; D002392:Catechin