Enantioselective Pd-Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2-a]indolone Substrates: Efficient Syntheses of (−)-Goniomitine, (+)-Aspidospermidine, and (−)-Quebrachamine
Beau P. Pritchett
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorJun Kikuchi
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorDr. Yoshitaka Numajiri
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Brian M. Stoltz
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorBeau P. Pritchett
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorJun Kikuchi
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorDr. Yoshitaka Numajiri
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Brian M. Stoltz
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 101-20, Pasadena, CA, 91125 USA
Search for more papers by this authorGraphical Abstract
Magnum (DH)PI: Application of dihydropyrido[1,2-a]indolone (DHPI) substrates in Pd-catalyzed asymmetric allylic alkylation chemistry enables rapid access to multiple alkaloid frameworks in an enantioselective fashion. The first catalytic enantioselective total synthesis of (−)-goniomitine, along with divergent formal syntheses of (+)-aspidospermidine and (−)-quebrachamine are reported.
Abstract
The successful application of dihydropyrido[1,2-a]indolone (DHPI) substrates in Pd-catalyzed asymmetric allylic alkylation chemistry facilitates rapid access to multiple alkaloid frameworks in an enantioselective fashion. Strategic bromination at the indole C3 position greatly improved the allylic alkylation chemistry and enabled a highly efficient Negishi cross-coupling downstream. The first catalytic enantioselective total synthesis of (−)-goniomitine, along with divergent formal syntheses of (+)-aspidospermidine and (−)-quebrachamine, are reported herein.
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