Development of (trimethylsilyl)ethyl ester protected enolates and applications in palladium-catalyzed enantioselective allylic alkylation: intermolecular cross-coupling of functionalized electrophiles.
The development of (trimethylsilyl)ethyl ester protected enolates is reported. The application of this class of compounds in palladium-catalyzed asymmetric allylic alkylation is explored, yielding a variety of α-quaternary six- and seven-membered ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to traditional β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of (trimethylsilyl)ethyl β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, MC 101-20, Pasadena, California 91125, United States.
Corey M
CM
Reeves
Douglas C
DC
Behenna
Brian M
BM
Stoltz
D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D004952:Esters; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
C000591753:(trimethylsilyl)ethyl ester; D000498:Allyl Compounds; D004952:Esters; D014297:Trimethylsilyl Compounds; D010165:Palladium