Michael addition of malononitrile

Scheme 6.69 Products obtained from the 12-catalyzed asymmetric Michael addition of malononitrile, nitromethane, and methyl a-cyanoacetate to N-cinnamoylbenzamide derivatives (acylic imides) and 12-catalyzed derivatization of the Michael adduct.

Scheme 6.70 Mechanistic proposal for the 12-catalyzed asymmetric Michael addition of malononitrile to (J-aryl and alkyl substituted N-acyl pyrrolidinones (cyclic imide) (A) and to a,P-unsaturated N-aryl substituted 2-methoxybenzamides such as N-cinnamoyl-2-methoxybenzamide (acyclic imide) (B).

Aminonaphtho[l,2-b]pyrans are converted into 5,6-dihydrobenzo[h]quinolines under basic conditions through a Dimroth rearrangement. The oxygen heterocycle is formed by a Michael addition of malononitrile to a 2-arylidene-l-tetralone and the whole sequence provides an... 

The tosylate 191 was synthesized from the malononitrile 194 obtained in modest yield by potassium fluoride catalyzed Michael addition of malononitrile to 3,6, trimethyl-2-cyclohexenone. A series of unexceptional steps led from 194 to 191 obtained in overall yield of 26%. 

Scheme 4.31 Enantioselective Michael addition of malononitrile and cyanosulfones to enones.

Scheme 4.43 Enantioselective Michael addition of malononitrile, methyl cyanoace-tate and nitromethane to M-enoylimides.

Scheme 7.8 Enantioselective Michael addition of malononitrile to trans-chalcones catalysed by prolinol Ij.

The enantioselective Michael addition of malononitrile CH2(CN)2 to trans-chalcones R CH=CHCOR catalysed by diarylprolinols (151), has been studied in detail. Both experimental and computational results are consistent with a bifunctional non-covalent activation of the reactants (152). The latter mechanism correctly predicts formation of the (R)-configured products (<75% eef- but is in conflict with the generally accepted iminium mechanism. Furthermore, (151) is likely to form the corresponding oxazolidine derivative as an intermediate, which has not been taken into account. 

Gonzalez R, Martin N, Seoane C, Marco JL, Albert A, CanoFH (1992) The first asymmetric synthesis of polyfunctionalized 4 Lf-pyrans via Michael addition of malononitrile to 2-acyl acrylates. Tet Lett 33 3809-3812... 

Scheme 1.16 Michael additions of malononitrile to a,P-unsaturated imides catalysed by a tertiary amine thiourea.

Scheme 1.23 Michael additions of malononitrile to o,P-unsaturated ketones catalysed by cinchona alkaloid-derived primary amine.

Scheme 19.22 Asymmetric Michael additions of malononitrile and methyl cyanoacetate to a,p-unsaturated imides catalysed by [(salen)Al]20.

Scheme 19.25 Asymmetric Michael additions of malononitrile to chalcones catalysed by Al-quinine complex.

Michael addition of malononitrile and cyanoesters to a, -unsaturated 2-acylimida-zoles, catalysed by a complex of double-stranded DNA and copper(II), has been reported to proceed with <84% eeP ... 

Jacobsen and coworkers reported Michael addition of malononitrile and non-substituted/substituted cyanoacetates to a,P-unsaturatedimides catalyzed by [(S,S)-salenAl]20 (67d) (Scheme 6.94) [llObj. 

A chiral quinine-derived squaramide catalysed the highly enantioselective Michael addition of malononitrile to chalcones. The reactions take place at a very low catalyst loading (0.5 mol%) and provide the Michael adducts with high yields and good enan-tioselectivities (up to 96% ee). Chiral bifunctional squaramides have also been used as multiple hydrogen-bond donor-acceptor organocatalysts for the asymmetric Michael addition of nitroolefins to 1,3-dicarbonyl compounds. ... 

The Michael addition of malononitrile and/or ethyl cyanoacetate (386) to nitrostyrenes has been reported to proceed in water at 80 C over 3h. In the presence of an orthohydroxy group, as in (385), the reaction is complete within 12 h at 40 C and gives rise to 2-amino-2-chromene derivatives (387) as a result of the subsequent cyclization. ... 

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