Expanding Insight into Asymmetric Palladium-Catalyzed Allylic Alkylation of N-Heterocyclic Molecules and Cyclic Ketones
Eeny, meeny, miny … enaminones! Lactams and imides have been shown to consistently provide enantioselectivities substantially higher than other substrate classes previously investigated in the palladium-catalyzed asymmetric decarboxylative allylic alkylation. Several new substrates have been designed to probe the contributions of electronic, steric, and stereoelectronic factors that distinguish the lactam/imide series as superior alkylation substrates (see scheme). These studies culminated in marked improvements on carbocyclic allylic alkylation substrates.
Additional Information© 2013 Wiley-VCH Verlag GmbH & Co. Issue published online: 20 Mar 2013. Article first published online: 27 Feb 2013. Manuscript Received: 12 Nov 2012. The authors thank NIH-NIGMS (R01 M080269-01), Roche, Abbott Laboratories, Amgen, Boehringer Ingelheim, the Gordon and Betty Moore Foundation, and Caltech for awards and financial support. D.C.D. thanks the National Science Foundation for financial support (Predoctoral Research Fellowship, No. DGE-1144469). W.-B.L. thanks the Shanghai Institute of Organic Chemistry for financial support (SIOC Postdoctoral Fellowship). A.N.M. is grateful for a fellowship by the Deutsche Akademie der Naturforscher Leopoldina. Profs. Sarah Reisman and Theodor Agapie are acknowledged for helpful discussions and suggestions. Dr. David VanderVelde and Dr. Scott Ross are acknowledged for NMR assistance. Dr. Mona Shahgoli and Naseem Torian are acknowledged for High-Resolution Mass Spectrometry assistance.
Accepted Version - nihms521643.pdf
Supplemental Material - chem_201300030_sm_miscellaneous_information.pdf