title: Sterically biased 3,3-sigmatropic rearrangement of chiral allylic azides: application to the total syntheses of alkaloids.
abstract: 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.
authors.affiliation: Université de Sherbrooke, Département de Chimie, 2500 Boulevard Université, Sherbrooke, Quebec, Canada, J1K 2R1.
authors.forename: Sophie
authors.initials: S
authors.lastname: Lauzon
authors.forename: François
authors.initials: F
authors.lastname: Tremblay
authors.forename: David
authors.initials: D
authors.lastname: Gagnon
authors.forename: Cédrickx
authors.initials: C
authors.lastname: Godbout
authors.forename: Christine
authors.initials: C
authors.lastname: Chabot
authors.forename: Catherine
authors.initials: C
authors.lastname: Mercier-Shanks
authors.forename: Stéphane
authors.initials: S
authors.lastname: Perreault
authors.forename: Hélène
authors.initials: H
authors.lastname: DeSève
authors.forename: Claude
authors.initials: C
authors.lastname: Spino
mesh_terms: 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
chemical_list: D000470:Alkaloids; D000498:Allyl Compounds; D000596:Amino Acids; D001386:Azides; D006571:Heterocyclic Compounds; D010880:Piperidines; D011804:Quinolines; C063984:lentiginosine; C011093:pumiliotoxin C; C007112:coniine