Sterically biased 3,3-sigmatropic rearrangement of chiral allylic azides: application to the total syntheses of alkaloids.
We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carbo- or heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.
Lauzon
Sophie
S
Université de Sherbrooke, Département de Chimie, 2500 Boulevard Université, Sherbrooke, Quebec, Canada, J1K 2R1.
Tremblay
François
F
Gagnon
David
D
Godbout
Cédrickx
C
Chabot
Christine
C
Mercier-Shanks
Catherine
C
Perreault
Stéphane
S
DeSève
Hélène
H
Spino
Claude
C
D000470:Alkaloids / Q000138:chemical synthesis*; D000498:Allyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D000596:Amino Acids / Q000138:chemical synthesis; D000818:Animals; D001386:Azides / Q000138:chemical synthesis / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis; D010880:Piperidines / Q000138:chemical synthesis; D011804:Quinolines / Q000138:chemical synthesis; D013237:Stereoisomerism
D000470:Alkaloids; D000498:Allyl Compounds; D000596:Amino Acids; D001386:Azides; D006571:Heterocyclic Compounds; D010880:Piperidines; D011804:Quinolines; C063984:lentiginosine; C011093:pumiliotoxin C; C007112:coniine