Reactivity and Synthetic Applications of 4,5-Dicyanopyridazine An Overview 英文参考文献.docVIP

Molecules 2010, 15, 1722-1745; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Review Reactivity and Synthetic Applications of 4,5-Dicyanopyridazine: An Overview ? Renzo Alfini, Marco Cecchi and Donatella Giomi * Laboratorio di Progettazione, Sintesi e Studio di Eterocicli Biologicamente Attivi (HeteroBioLab), Dipartimento di Chimica, Università di Firenze, Polo Scientifico e Tecnologico, Via della Lastruccia 3/13, I-50019 Sesto Fiorentino, Italy; E-Mail: renzo.alfini@unifi.it (R.A.) * Author to whom correspondence should be addressed; E-Mail: donatella.giomi@unifi.it; Tel.: +39-0554573475; Fax: +39-0554573575. ? Dedicated to Prof. Rodolfo Nesi on the occasion of his 70th anniversary. Received: 28 December 2009; in revised form: 12 February 2010 / Accepted: 5 March 2010 / Published: 12 March 2010 Abstract: Despite the poor reputation of electron-deficient pyridazines in intermolecular Hetero Diels-Alder (HDA) reactions, 4,5-dicyanopyridazine (DCP) showed a surprising reactivity as a heterocyclic azadiene in inverse electron-demand HDA processes with different dienophiles. The use of alkenes, alkynes and enamines as 2π electron counterparts afforded dicyanocyclohexa-1,3-dienes and substituted phthalonitriles, respectively, while the use of suitable bis-dienophiles provides a general strategy for the one-pot synthesis of polycyclic carbo- and hetero-cage systems through pericyclic three-step homodomino processes. HDA reactions with heterocyclic dienophiles allowed direct benzoannelation: in particular, pyrrole and indole derivatives were converted to dicyano-indoles and -carbazoles. In addition an unprecedented reactivity of DCP as a very reactive heterocyclic electrophile at the C-4 carbon was also evidenced: by changing the experimental conditions, cyanopyrrolyl- and cyanoindolyl-pyridazines were obtained through rea