NOVEL REACTION OF AMINOPYRIDINES WITH GLYOXAL AND FORMALDEHYDE - SYNTHESIS OF 4,8-DI(N-AMINOPYRIDYL)2,6-DIOXA 4,8-DIAZABICYCLO[3.3.0]OCTANE, 6,8-DI(N-AMINOPYRIDYL)2,4-DIOXA 6,8-DIAZABICYCLO[3.3.0]OCTANE AND X-RAY STRUCTURAL STUDY OF RELATED 1,3-DI(N-AMINOPYRIDYL)4,5-DIHYDROXY IMIDAZOLIDINE
Smf. Farnia et al., NOVEL REACTION OF AMINOPYRIDINES WITH GLYOXAL AND FORMALDEHYDE - SYNTHESIS OF 4,8-DI(N-AMINOPYRIDYL)2,6-DIOXA 4,8-DIAZABICYCLO[3.3.0]OCTANE, 6,8-DI(N-AMINOPYRIDYL)2,4-DIOXA 6,8-DIAZABICYCLO[3.3.0]OCTANE AND X-RAY STRUCTURAL STUDY OF RELATED 1,3-DI(N-AMINOPYRIDYL)4,5-DIHYDROXY IMIDAZOLIDINE, Tetrahedron, 53(7), 1997, pp. 2557-2564
Condensation of 2-aminopyridine with glyoxal proceeds with high select
ivity to a mixture of meso and dl diol 7 to be easily transformed into
the corresponding bicyclooctane 2a and 3a with formaldehyde and aceto
nitrile as solvent. In water, however, the reaction selectively produc
es imidazolidine 4a. Based on NMR analysis, the major diastereomers we
re assigned as syn derivatives. X-ray crystal structure of 4a shows a
planar configuration for imidazolidine ring, in line with two anomeric
effects, first a strong n(N) --> sigma(C-O) interaction and second a
weak n(O) --> sigma(C-N) one. A network of hydrogen bonding between
pyridyl nitrogens and hydroxy hydrogens forms a pattern of twelve atom
in a chair-like conformation. (C) 1997, Elsevier Science Ltd.