Malononitriles isatylidene

Keywords Isatylidene malononitriles, a-azido ketones, ethanol, piperidine, room temperature, one-pot domino process, 3-(aminomethylene)oxindoles... 

To a stirred solution of isatylidene malononitrile (1 1 mmol) and a-azido ketone (2 1.25 mmol) in EtOH (5 mL) was added piperidine (1.0 mmol), and stirring was continued... 

Kamalraja, J., Hari Babu, T., Muralidharan, D., and Perumal, P. T. (2012). A facile method for the synthesis of 3-(aminomethylene)oxindoles from isatylidene malononitriles and a-azido ketones. Synlett, 23, 1950-1954. 

In the second reaction, a Michael-Michael cascade between an unsaturated oxin-doles 17 and enones 22 was shown to be catalyzed by a primary amine-derived catalyst (II) (Scheme 10.3). The reaction afforded the spirooxindoles 23 in excellent yields and diastereo and enantioselectivities. Wang used a similar approach in the reaction of isatylidene malononitriles and enones [12]. The reaction was catalyzed by the dual combination of cinchona-based chiral primary amine and BINOL phosphoric acids to afford the spirocycles in excellent yields (88-99%), diastereo (up to 99 1 dr), and enantioselectivities (95-99% ee). 

In 2011, Shi and coworkers reported a complementary [3+2] cycloaddition of MBH carbonates 42 with isatylidene malononitriles 43 [19]. They reported a simple example of the enantioselective version of this reaction that used a chiral phosphine bearing a thiourea moiety VII as the catalyst and afforded the product 44 in good yield and stereoselectivity (Scheme 10.13). 

Deng, H.-R, Wei, Y, Shi, M., (2011). Highly regio- and diastereoselective construction of spirocyclopenteneoxindoles through phosphine-catalyzed [3 -l- 2] annulation of Morita-Baylis-Hillman carbonates with isatylidene malononitriles. Organic Letters, 13, 3348-3351. 

Han, Sheng and Yan described the synthesis of triphenylphos-phanylidene spiro[cyclopentane-l,3 -indolines] and spiro[cyclopent[2]ene-l,3 -indolines] via three-component reactions of triphenylphosphine, isatylidene malononitrile(ethyl cyanoacetate) and but-2-ynedioate or hex-2-en-4-ynedioate, respectively (Fig. 7). ... 

Very recently, the combination of a cinchona-based chiral primary amine and a chiral phosphoric acid has been demonstrated by Wang and coworkers [36] as a powerful and synergistic catalyst system for the double Michael addition of isatylidene malononitriles with a,P-unsaturated ketones (Scheme 43.23). Various novel chiral spiro[cyclohexane-l,3 -indoline]-2, 3-diones were obtained in high... 

Scheme 43.23 Double Michael addition of isatylidene malononitriles catalyzed by primary amine/phosphoric acid.

Compounds of the type 171 can generally be easily dehydrated and many reactions of isatins lead directly to isatylidene derivatives. Use of active methylene compounds such as malononitrile and cyano-acetate gave compounds of the type 184. Various 4-thiazolidones have been condensed with isatin, generally under acidic conditions, to give 185. " Similar type compounds (186) have been obtained from thianaphthenes and isatin using acetic acid. " These compounds (186) have been used as dyes. Other heterocyclic ketones... 

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