Diethyl malonate anion

Stable enolates such as diethyl malonate anions react with allyl sulfones (or acetates) in the presence of nickel complexes to give a mixture of the a- and /-product83. The regioselectivity is generally poor in the nickel-catalyzed reaction, but the molybdenum-catalyzed reaction is selective for alkylation at the more substituted allylic site, thereby creating a quaternary carbon center84. 

Kinetic studies have been infrequent but Cundall (45) reported recently on the system acrylonitrile-DMF-sodium diethyl malonate. Designating the diethyl malonate anion as C and the DMF solvent as XH he showed that the rate expression is ... 

Ethoxyvinyl)oxiranes are attacked by the diethyl malonate anion regioselectively, rather than regiospecifically <85izv6825>, giving rise to mixtures of isomeric y-lactones <92KGS22>. 

Sodium hydride (60% oil dispersion, 0.15 g, 0.38 mmol) was washed with hexane (2x2 mL) and THF (1x2 mL). Note exercise great care with NaH, particularly after the hexane wash the NaH should be kept under nitrogen or argon.) To a suspension of oil-free sodium hydride in THF (5mL) was added diethylmalonate (0.770 mL, 0.38 mmol). After 15 min of stirring, the resulting diethyl malonate anion solution was added via a cannula to a solution of the allylic benzoate (131 mg, 0.56 mmol), Pd(PPh3)4 (45 mg, 0.039 mmol), and triphenylphosphine (100 mg. 

In 5-chloro-l,3-dimethyl-6-nitropyrido[2,3-c/]pyrimidine-2,4(l//,3//)-dione the halogen group reacts with diethyl malonate anion to yield the corresponding substituted malonic ester.352... 

Mechanism. Diethyl malonate by reaction with the basic piperidine results into the formation of the resonance stabilized diethyl malonate anion as given below ... 

Consequently, the diethyl malonate anion adds on to the carboxyl function of salicylaldehyde, and then the intermediate alkoxide formed is duly protonated to yield the addition product as shown below ... 

Microwaves Alkylation of ethylphenyl sulfonyl acetate, diethyl malonate, anions derived from active methylene Dihalocyclopropanation of substituted olefins under LLPTC and SLPTC conditions Ethoxylation of o,p-nitrochlorobenzene Reactions of carboxylic acids with halides Wang and Jiang (1992), Wang et al. (1995) Villemin and Labiad (1992) Yuan et al. (1992a) Yuan et al. (1992b)... 

Heerden and co-workers have reported a convenient synthesis of multifunctional stereodefined dienes 187 using substituted diethyl malonate anions and MBH adducts 186, which were derived from a,p-unsaturated aldehydes (Scheme 3.74). 

An early example of aryne insertion into C—C single bonds was described by Guyot et al. in the addition of diethyl malonate anion to arynes and the subsequent rearrangement to homophthalic esters, such as 33 (Scheme 12.13) [30]. However, the reported yield was quite low and the desired product accompanied by numerous undesirable side products. 

The displaconent with invonon of the protected sugar doivatives bearing a 4 0-tiiflate group with cyanide or diethyl malonate anions to produce 4-C-branched-chain sugars has been described. ... 

Transformation b converts the cyclohexanone alpha carbon to an electrophile by brominating that position. An Sn2 with the stabilized diethyl malonate anion add the required two-carbon chain. As in a, the synthesis of the TM concludes with hydrolysis of the diester, decarboxylation, and reesterification. 

Steroidal a,jS-unsaturated ketones can be dehydrogenated, via n-allyl complexes, to give conjugated dienones. Decomposition of the Jt-allyl complex can be effected either thermally (Howsam and McQuillin, 1968) or by treatment with diethyl malonate anion or cyanide ion (Harrison et al, 1969). 

The first example of an allylic alkylation catalyzed by iron compounds was reported in 1979. Allylic halides and carboxylates are treated with a diethyl malonate anion in the presence of sodium tricarbonyl(nitrosyl)ferrate to give the allylated malonates with good regioselectivity in favor of the ipso product (Scheme 4-195). This transformation can be carried out in a carbon monoxide atmosphere catalyzed by the Hieber-type complex [Bu4N][Fe(CO)3NO] (TBAFe) that is easier to handle. The... 

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