Synthetic approaches to racemic porantheridine and 8-epihalosaline via a nitroso Diels-Alder cycloaddition/ring-rearrangement metathesis sequence.
The application of a sequence involving a nitroso Diels-Alder cycloaddition and a ring-rearrangement metathesis to the total synthesis of (+/-)-8-epihalosaline and the formal synthesis of (+/-)-porantheridine is described. The formation of the 2,6-trans-disubstituted piperidine backbone of porantheridine has been accomplished by addition of a Grignard reagent onto an N-benzylpiperidone followed by a highly diastereoselective reduction of the imminium intermediate in one pot.
Sancibrao
Pierre
P
Laboratoire de Chimie des Procédés et Substances Naturelles, ICMMO, CNRS UMR 8182, Bât 410, Université de Paris-Sud-11, F-91405 Orsay, France.
Karila
Delphine
D
Kouklovsky
Cyrille
C
Vincent
Guillaume
G
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000737:chemistry*; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
C552161:8-epihalosaline; D000470:Alkaloids; D009603:Nitroso Compounds; D010880:Piperidines; C450779:porantheridine