Naslov
Molecular structures and ab initio molecular orbital calculations of the optically active derivatives of 1-aminocyclopropane-1-carboxylic acid

Autori
Džolić, Zoran ; Cetina, Mario ; Kovaček, Damir ; Hergold-Brundić, Antonija ; Mrvoš-Sermek, Draginja ; Nagl, Ante ; Slade, Neda ; Pavelić, Krešimir ; Balzarini, Jan ; De Clercq, Erik ; Zerbe, Oliver ; Folkers, Gerd ; Scapozza, Leonardo ; Mintas, Mladen

Izvornik
Journal of molecular structure (0022-2860) 655 (2003), 2; 229-241

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
1-aminocyclopropane-1-carboxylic acid derivatives ; synthesis ; rearrangement ; ab initio MO calculations ; density functional theory ; single crystal X-ray analysis ; cytostatic activities ; antiviral activities

Sažetak
The novel optically active derivatives of 2, 2'-disubstituted-1-aminocyclopropane-1- carboxylic acid (-)-2 and (+)-3 weresynthesized from the spiro-azlactone(+)-1. Oxidation of the diol moiety of (+)-3 gave by ring enlargement the racemic mixture of 2, 3-dihydrofuran derivative (+/-)-6. This conversion is explained by stepwise rearrangement of the initially formed tetrasubstituted cyclopropanecarbaldehyde 4 through zwitterionic's reactive intermediate 5. The formation of (+/-)-6 is preferred energetically as established by ab initio calculations of the ground states and possible intermediates for that rearrangement. The crystal structure and absolute configuration of the compounds (+)-1, (-)-2, (+)-3 and (-)-7 were determined by single-crystal X-ray diffraction method. All four compounds possess Z-configuration of the cyclopropane ring. The dioxolane ring in the structures (+)-1 and (-)-2 adopts half-chair conformation, while the cyclopropane ring and geminally substituted groups in the structures (-)-2, (+)-3 and (-)-7 possess the anticlinal conformation. The molecules of the compound (+)-1 are connected by very weak intermolecular hydrogen bond of C-H...O type. In the compounds (-)-2, (+)-3 and (-)-7 inter- and intramolecular hydrogen bonds of N-H...O type were observed. The spiro-compound (+)-1 exhibited a more pronounced inhibitory activity against the proliferation of murine leukemia and human T-lymphocytes cells than other type of tumor cell lines and normal human fibroblast cells.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Temeljne medicinske znanosti, Kliničke medicinske znanosti

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