Dimethyl Malonate Anion Research Articles

Vinyl trifluorosulfonates in the carbopalladation of allenic hydrocarbons

The palladium-catalyzed reaction of an enol triflate, an allenic hydrocarbon, and the anion of dimethyl malonate leads to conjugated dienes 1 in good yield. No isomerisation is observed when this reaction is run with both triflates of 2-methylcyclohexanone.

Mechanism of the reaction of 1-methoxy- and 1-chloro-2,4,6-trinitrobenzene with dimethyl malonate anion

1H NMR spectra have been used to prove the formation of 1,3- and 1,1-adducts in the reaction of 1-methoxy-2,4,6-trinitrobenzene with dimethyl malonate anion and formation of 1,3-adduct in the analogous reaction of 1-chloro-2,4,6-trinitrobenzene. Dimethyl 2,4,6-trinitrophenylmalonate is formed from 1-chloro-2,4,6-trinitrobenzene at the same rate and by the same mechanism as the 1,1-adduct from 1-methoxy-2,4,6-trinitrobenzene. The two reactions only differ in their rate-limiting steps.

Studies on structurally simple butenolides. V. reactions of protoanemonin with piperidine and [formula omitted]-nucleophiles : A general approach to its behaviour as electrophilic acceptor

Reaction of protoanemonin, 1 , with piperidine, dimethyl malonate anion, and lithium dimethyl- and dibutylcuprates are reported. Thus, while in the first case almost no regioselectivity is observed, in the other cases the obtained products are the result of nucleophilic attack to the exocyclic C-C double bond of 1 exclusively, giving the 1,6-adduct in the first step of the reaction. These adducts can evolve, with participation of unreacted protoanemonin in the reaction conditions, to polycyclic compounds, through 1,6-addition, alkylation and intramolecular Michael addition processes. Constitution of the compounds obtained have been assigned on the basis of spectral characteristics and mechanistic approaches. The behaviour of 1 in front of nucleophiles has been rationalized and generalized by means of experimental results and theoretical calculations.

Nucleophilic displacement of activated aryl triflates a new synthesis of oxindoles and arylacetic acids

2-Nitroaryl triflates undergo efficient base-catalyzed nucleophilic displacement by dimethyl malonate anion to yield dimethyl nitroarylmalonates, which subsequently are converted in high yields to nitroarylacetic acids and oxindoles.

Reactions of 2,4,6-trinitrochlorobenzene with dimethyl malonate anion in methanol and methanol-dimethyl sulphoxide mixture

Reactions of 2,4,6-trinitrochlorobenzene with dimethyl malonate anion in methanol and methanol-dimethyl sulphoxide mixture

Synthesis and Polymerization of Trimethyl Bicyclobutane‐1,2,2‐Tricarboxylate

AbstractTrimethyl bicyclobutane‐1,2,2‐tricarboxylate (2) was synthesized by a facile five‐step route, beginning with the ferric chloride‐catalyzed addition of chloroform to methyl acrylate to give methyl 2,4,4‐trichlorobutyrate (3). Replacement of the 2‐chloro group by iodide was followed by displacement with dimethyl malonate anion to give trimethyl 4,4‐dichlorobutane‐1,1,2‐tricarboxylate (5a). Thermolysis of the corresponding sodium derivative 5b gave trimethyl cis, trans‐3‐chlorocyclobutane‐1,2,2‐tricarboxylate (6). Closure of the bicyclobutane ring to yield 2 was accomplished by potassium hydride in ether with methanol as catalyst.Bicyclobutane 2 polymerized under free radical initiation with breakage only of the 1,3‐bond. The homopolymers, obtained in moderate yields, were of low molecular weight, probably owing to steric hindrance effects. Copolymerization occurred with vinyl monomers of varying polarity. The copolymers, obtained in moderate yields, had low molecular weights and consisted mostly of the vinyl comonomer units.

Bicyclic bases Ambident anions as intramolecular nucleophiles in the formation of 2‐oxa‐5‐azabicyclo[2.2.1] heptane derivatives

AbstractThe intramolecular cyclization of the ambident anion 5 derived from condensation of N, O‐ditosylhydroxy‐L‐proline acid chloride with dimethyl malonate anion was studied under a variety of reaction conditions. Cyclization occurred solely by O‐alkylation to give 2‐oxa‐5‐azabicyclo[2.2.1 ]heptanes. The NMR speetra of the hicyclo compounds are diseussed.