Amino Heck Reactions of Oximes

Pyridines and quinolines are similarly prepared. The pyrrole 474 was obtained by 5-exo cyclization of 3-methoxy-l-phenyl-4-penten-l-one ( )-0-pentarfluoro-benzoyloxime 473 under usual conditions. On the other hand, 2-phenylpyridine (475) was obtained by 6-endo cyclization as the main product in the presence of n-Bu4NCl. Isoquinoline 477 was prepared in 77 % yield by 6-exo cyclization of the oxime 476 [179]. 

Substituted azaazulene 479 was prepared from cycloheptatrienylmethyl ketone O-pentafluorobenzyloxime 478 by Pd-P(r-Bu)3-catalyzed cyclization, followed by treatment with Mn02 [180]. As observed in the Heck reaction, the domino insertion of olefins occurred to produce the polycyclic imine 481 when the trienyloxime 480 was subjected to the Pd-catalyzed reaction [181]. 

As a related reaction, an N-Cl bond in unsaturated A-chloroamine undergoes oxidative addition to Pd(0) and eyclization. In the treatment of A-ehloro-2,2-dimethyl-4-pentenylamine 482 with Pd(PPh3)4 in the absence of a base, oxidative 

Hagiwara, Y. Shimizu, T. Hoshi, T. Suzuki, M. Ando, K. Ohkubo, and C. Yoko-yama. Tetrahedron Lett., 42,4349 (2001). 

Masllorens, M. Moreno-Manas, A. Pla-Quintana, R. Pleixats, and A. Roglans, Synthesis, 1903 (2002). 

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