Reaction of 2-Amino-6-aryl-4-(dicyanomethyl)-3-azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles with Primary and Secondary
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tion of 2-Amino-6-aryl-4-(dicyanomethyl)3-azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles with Primary and Secondary Amines I. N. Bardasova,*, A. Yu. Alekseevaa, A. A. Mikhailovb, and O. V. Ershova b
a Ul’yanov Chuvash State University, Cheboksary, 428015 Russia Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences (IGIC RAS), Moscow, 119991 Russia *e-mail: [email protected]
Received April 7, 2020; revised April 20, 2020; accepted April 28, 2020
Abstract—2-Amino-6-aryl-4-(dicyanomethylene)-3-azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles undergo transamination under the action of primary and secondary amines to form 2-(alkylamino)-6-aryl-4-(dicyanomethylene)3-azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles. Keywords: 3-azabicyclo[3.1.0]hexane, cyclopropane, pyrrolidin-2-one, cyano group, transamination
DOI: 10.1134/S107042802008014X
The chemistry of cyclopropane derivatives, even though their synthesis and properties are well documented, continues to develop rapidly. This is due to broad-range biological activity found in some cyclopropane derivatives [1–5] and high skeletal and functional synthetic potential of this class of compounds [6]. Cyano-substituted cyclopropanes feature especially diverse transformations, and, depending on the functional environment, they may lead to derivatives of pyridine [7, 8], pyrrole [9, 10], thiophene [11], furan [12–14], and pyridazine [15]. Cyclopropanes with electron-acceptor substituents readily react with various nucleophilic reagents, and, depending on the type of the nucleophile, either the cyclopropane carbon [7–14] or acceptor substituents [9, 13, 15] can be attacked. The presence of vicinal functional groups in a cyclopropane creates prerequisites for annulation to the three-membered ring of a pyrrole fragment to form 3-azabicyclo[3.1.0]hexane derivatives [8, 9, 16–19]. The interest in the synthesis of such compounds is due to the biological activity characteristic of some 3-azabicyclo[3.1.0]hexanes, among them the antibiotics trovafloxacin and indolizomycin, the analgesic bicifadine, the antiviral drug boceprevir, the natural antitumor anti-
biotics duocarmycin A and mitomycin, and the alkaloid cycloclavine [16]. We earlier showed that the reaction of bromo derivatives of methylene-active compounds with arylmethylidene derivatives of malononitrile dimer form polycyano-substituted 3-azabicyclo[3.1.0]hexanes [17–19] and established the steric structure of 2-amino6-aryl-4-(dicyanomethylene)-3-azabicyclo[3.1.0]hex2-ene-1,5-dicarbonitriles 1 by NOE spectroscopy [17]. It was shown that treatment of compounds 1 with acidic water results in either hydrolysis of the amino group or decyclization of the pyrrole ring [20]. In the present work we have studied the reactions of earlier synthesized 2-amino-6-aryl-4-(dicyanomethylene)-3-azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles 1 with primary and secondary amines (Scheme 1). As known, the reactions of cyclopropanes containing several electron-acceptor substituents with amines involve ring opening f
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