Fused triazoles via tandem reactions of activated Cinchona alkaloids with azide ion. Second Cinchona rearrangement exemplified.
[reaction: see text] Intramolecular 1,3-dipolar cycloadditions of cinchona azides to the C10-C11 alkyne and C10-C11 olefin unit of the alkaloid have been designed via tandem strategy. A variety of fused triazoles and triazolines with a bis-azahomotwistane skeleton have been prepared. In trifluoroethanol, O-mesylcinchonidine 7-OMs and NaN(3) furnish triazole 8 as well as cage-expanded 1,5-diazatricyclo[4.4.1.0(3,8)]undecane derivative 10. Both fused triazoles 8 and 10 are formed with retention of configuration at C9 and C3, respectively. 1-Azabicyclo[3.2.2]cage expansion is shown to be reversible.
Röper
S
S
Department of Organic Chemistry, University of Hannover, Schneiderberg 1B, 30167 Hannover, Germany.
Franz
M H
MH
Wartchow
R
R
Hoffmann
H M R
HM