Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones.
The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF3)3-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee's up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Robert A
RA
Craig
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Steven A
SA
Loskot
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Justin T
JT
Mohr
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Douglas C
DC
Behenna
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Andrew M
AM
Harned
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
Brian M
BM
Stoltz
D000478:Alkylation; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry* / Q000302:isolation & purification*; D008024:Ligands; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D003517:Cyclopentanes; D008024:Ligands; C007201:cyclopentanone; D010165:Palladium