Synthesis of beta- and gamma-carbolines by the palladium-catalyzed iminoannulation of alkynes.
A variety of substituted beta- and gamma-carbolines have been prepared in moderate to excellent yields by the palladium-catalyzed annulation of internal and terminal acetylenes by the tert-butylimines of N-substituted 3-iodoindole-2-carboxaldehydes and 2-haloindole-3-carboxaldehydes, respectively. This annulation chemistry is effective for a wide range of alkynes, including aryl-, alkyl-, hydroxymethyl-, ethoxycarbonyl-, and trimethylsilyl-substituted alkynes. When an unsymmetrical internal alkyne is employed, this method generally gives two regioisomers. When a terminal alkyne is employed, only one regioisomer has been isolated. This palladium-catalyzed annulation chemistry has also been successfully applied to the synthesis of two biologically interesting beta-carboline alkaloids, ZK93423 and abecarnil (ZK112119).
Zhang
Haiming
H
Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
Larock
Richard C
RC
D000470:Alkaloids / Q000138:chemical synthesis*; D000480:Alkynes / Q000737:chemistry*; D002243:Carbolines / Q000032:analysis / Q000138:chemical synthesis*; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D007211:Indoles / Q000138:chemical synthesis*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D000470:Alkaloids; D000480:Alkynes; D002243:Carbolines; D007211:Indoles; D010165:Palladium; C042569:ZK 93423; C062769:abecarnil