Catalytic N-sulfonyliminium ion-mediated cyclizations to alpha-vinyl-substituted isoquinolines and beta-carbolines and applications in metathesis.
[reaction: see text] Catalytic Sn(OTf)2-induced cyclization of linear, aryl-containing allylic N,O-acetals produced vinyl-substituted tetrahydroisoquinolines and tetrahydro-1H-beta-carbolines. The usefulness of the vinyl moiety in the resulting products was demonstrated via the synthesis of various key building blocks for alkaloid structures. The alpha-vinyl moiety was utilized in a [2,3] sigmatropic rearrangement, in ring-closing metathesis and a cross-metathesis-based synthesis of vincantril, an antianoxia agent, and a synthetic member of the vincamine type natural products.
J. H. van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 129, NL-1018 WS Amsterdam, The Netherlands.
Sape S
SS
Kinderman
Monique M T
MM
Wekking
Jan H
JH
van Maarseveen
Hans E
HE
Schoemaker
Henk
H
Hiemstra
Floris P J T
FP
Rutjes
D000470:Alkaloids / Q000138:chemical synthesis*; D002243:Carbolines / Q000138:chemical synthesis*; D002384:Catalysis; D003500:Cyclization; D000860:Hypoxia; D007097:Imines / Q000737:chemistry*; D007546:Isoquinolines / Q000138:chemical synthesis*; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D000470:Alkaloids; D002243:Carbolines; D007097:Imines; D007546:Isoquinolines; C482356:N-sulfonylimine; D013450:Sulfones; D014753:Vinyl Compounds