Enantioselective Pd-Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2-a]indolone Substrates: Efficient Syntheses of (-)-Goniomitine, (+)-Aspidospermidine, and (-)-Quebrachamine.
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.
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.
Beau P
BP
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.
Jun
J
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.
Yoshitaka
Y
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. stoltz@caltech.edu.
Brian M
BM
Stoltz
D000478:Alkylation; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D007211:Indoles / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D011804:Quinolines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000498:Allyl Compounds; D026121:Indole Alkaloids; D007211:Indoles; D011725:Pyridines; D011804:Quinolines; C409672:aspidospermidine; C000628189:dihydropyrido(1,2-a)indolone; C526621:goniomitine; D010165:Palladium; C091897:quebrachamine
alkaloids; allylic alkylation; asymmetric catalysis; quaternary centers; total synthesis
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