Enantioselective Total Syntheses of (-)-Rhazinilam, (-)-Leucomidine B, and (+)-Leuconodine F.
A divergent total synthesis of three structurally distinct natural products from imine 9 was accomplished through an approach featuring: 1) a Pd-catalyzed decarboxylative cross-coupling, and 2) heteroannulation of 9 with bromoacetaldehyde and oxalyl chloride to give tetrahydroindolizine 6 and dioxopyrrole 7, respectively. The former was converted into (-)-rhazinilam, while the latter was converted into (-)-leucomidine B and (+)-leuconodine F. A substrate-directed highly diastereoselective reduction of a sterically unbiased double bond by using a homogeneous palladium catalyst was developed. A self-induced diastereomeric anisochronism (SIDA) phenomenon was observed for leucomidine B.
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch.
Dylan
D
Dagoneau
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch.
Zhengren
Z
Xu
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch.
Qian
Q
Wang
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch. jieping.zhu@epfl.ch.
Jieping
J
Zhu
D000470:Alkaloids / Q000138:chemical synthesis*; D007212:Indolizines / Q000138:chemical synthesis*; D007769:Lactams / Q000138:chemical synthesis; D013237:Stereoisomerism
D000470:Alkaloids; D007212:Indolizines; D007769:Lactams; C000611351:leucomidine B; C000611352:leucomidine F; C009170:rhazinilam
asymmetric synthesis; divergent synthesis; domino cyclization; heteroannulation; indole alkaloids