Sodium diethyl malonate

Reaction of o-toluidine with chloral hydrate in presence of hydroxylamine hydrochloride and subsequent treatment with H2SO4 gave the isatin derivative 337. Bromination of 337 followed by reaction with sodium diethyl malonate gave 338. Catalytic reduction with Pd/C gave the oxoindole derivative 339 that upon hydrolysis with aqueous NaOH followed by... 

The research group of Van Leeuwen reported the use of carbosilane de-ndrimers appended with peripherial diphenylphosphino end groups (i.e. 25, Scheme 26) [37]. After in situ complexation with allylpalladium chloride, the resultant metallodendrimer 25 was used as catalyst in the allylic alkylation of sodium diethyl malonate with allyl trifluoroacetate in a continuous flow reactor. Unlike in the batch reaction, in which a very high activity of the dendrimer catalyst and quantitative conversion of the substrate was observed, a rapid decrease in space time yield of the product was noted inside the membrane reactor. The authors concluded that this can most probably be ascribed to catalyst decomposition. The product flow (i.e. outside the membrane reactor)... 

In the Michael addition reaction depicted in eq. [146] the diastereomeric sulfoxides 312 are formed under kinetic control conditions, therefore, the addition of sodium diethyl malonate is an irreversible process. On the contrary, addition of sodium methoxide to the sulfoxide 311 is a thermodynamically controlled process and leads to a mixture of diastereomeric ]3-methoxysulfoxides 313 in a 31 69 ratio (320). 

For further details of this reaction, the reader is referred to Chapter 9. The catalytic allylation with nucleophiles via the formation of Ti-allyl metal intermediates has produced synthetically useful compounds, with the palladium-catalyzed reactions being known as Tsuji-Trost reactions [31]. The reactivity of Ti-allyl-iridium complexes has been widely studied [32] for example, in 1997, Takeuchi idenhfied a [lrCl(cod)]2 catalyst which, when combined with P(OPh)3, promoted the allylic alkylation of allylic esters 74 with sodium diethyl malonate 75 to give branched... 

Cooling below 0°C will induce precipitation of the sodium diethyl malonate. 

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 ... 

The tricyclic furo-fused 1,2,4-triazinium salt (74 X= O) reacts with nucleophiles such as sodium hydrogen sulfide, sodium diethyl malonate, or sodium ethyl cyanoacetate to yield the new ring systems thieno[2,3-e pyrido[l,2-Z>]-l,2,4-triazinium perchlorate (74 X= S) and cyclopenta(e]pyrido[ 1,2-b -1,2,4-triazines (75) [94CB1799]. 

Treatment of enantiomerically pure (5, S)-121 with dibenzylamine or sodium diethyl malonate in the presence of palladium(O) gave the essentially enantiomerically pure (ee > 98%) products (S)-191 (Nu = Bn2N) and (5)-191 (Nu = CH(C02Et)2), respectively (Table 12). 

Nucleophiles A, dibenzylamine, B, sodium diethyl malonate, C, lithium salt of tert-butyl N-(diphenylmethylene)glycinate. 

Vierfond et al. used thermal cyclization (79JHC753). The anion obtained by the reaction of quinaldine with phenyllithium was reacted with o-chlorobenzonitrile to afford imine 138, which cyclized at 235°C to give amino derivative 139 (32%). Another method is shown by the reaction of 140-142. The reaction of 140 with excess sodium diethyl malonate in hexamethylphosphoramide (HMPA) at 190°C gave cyclization product 141 (38%), which was converted to fully aromatic 142 by reaction with acetic anhydride (92%) (82JHC127). 

Condensation of alkynylquinoxalines (see Section 6.3.2.1.4.5.) with sodium diethyl-malonate and related compounds yields pyrido[l,2-a]quinoxalin-4-one derivatives, and 2-chloro-... 

Michael, A. Addition of sodium acetoacetate and sodium diethyl malonate to unsaturated acids. J. Prakt. ChemJChem.-Ztg. 1894, 49, 20. 

Methylation of iminothiazolines (175) followed by reaction with NaHSe gives 2-selenoxo-thiazolines (176) (Equation (27)) <84PJC447>. 3-Alkyl-2-(A-cyanoimino)thiazolidines (177) are methylated with trimethyloxonium tetrafluoroborate the resulting nitrilium salts react with sodium diethyl malonate to afford methylenethiazolidines (178) and urea derivatives (179) along with the iminothiazolidines (180) (Equation (28)) <93H(36)55>. 

Due to steric reasons, conduritol-B peracetate gives exclusively the monoalkylated product 3362. Since the reaction proceeds through a nteso-tt-allyl complex a racemic compound results which is a suitable precursor for the synthesis of branched-chain cyclitols. The reaction with sodium diethyl malonate in tetrahydrofuran gives the same selectivity, independent of the enantiomeric purity of the starting material, but exhibits a reduced rate. 

Ethane-tetracarboxylic ester from sodium-diethyl-malonic ester. 

Shimizu and Tsujit and Cazes, Gore, and co-workers reported the first examples of such transformations in 1984. The Pd(0)-catalyzed reactions of either an aryl halide (bromide or iodide) or an alkenyl bromide with a 1,2-diene in the presence of sodium diethyl malonate afforded styrene derivatives 24 and 1,3-diene derivatives 25, respectively (Scheme... 

The rearrangement of a-sulfonimidoyl-/3,y-unsaturated esters paved the way for a promising synthesis of y-amino acids in fair yields (Scheme 24). In the presence of a chiral ligand, such as BINAP, moderate asymmetric induction has been reported (20-60% ee). The demonstrated leaving capability of the sufoximino group has been utilized in allylic substitution with typical nucleophiles, such as sodium diethyl malonate, dibenzy-lamine, and t-butyl N-(diphenyhnethylene)glycinate. ... 

Nncleophilic attack by carbanions on Pd rr-complexes provides an excellent method for carbon-carbon bond formation. The first example of natural product synthesis by the reaction of Pd rr-complex with carbon nucleophiles appears to be Holton s synthesis of prostanoids via treatment of an allylic amine with the stoichiometric amount of lithinm tetrachloropalladate and sodium diethyl malonate, followed by addition of diisopropy-lethylamine, which led to the formation of an isomerically pure bicyclic Pd-amine complex in 92% yield " (Scheme 18). The carbon nucleophile ends up a and trans to the dimethylamino group. Both regio- and stereochemistries must be controlled by the Me2N group. The amino diester intermediate was further transformed into Corey lactone diol, which had previously been converted to PGp2a in two steps and 80% overall yield. 

Prepared by Snyder et al, (742) from sodium diethyl malonate and gramine metbiodide. 

The a-carboxymethyl caprolactam was obtained from a-bromo-caprolactam via nucleophilic substitution employing sodium diethyl malonate (3), whereas both 3-carboxymethyl caprolactam uid 4-carboxymethyl-2-piperldone were synthesized via nucleophilic addition of the malonate euiibne to the corresponding a, 3 unsaturated lactam (4,S). The 4-carboxy-methyl-2-pyrrolidone was obtained by hydrolysis of the corresponding ethyl ester which was synthesized according to the procedures given by Henecka et al. (6.S). 

A novel regiospecific synthesis of islandicin was described by Glein etal. 145) (Scheme 21). Thus Fries rearrangement of l-propionyloxy-5-methoxynaphthalene followed by methylation and bromination yielded the ketone (172). Alkylation with sodium diethyl malonate followed by demethylation, ester hydrolysis and decarboxylation gave the acid (173). Elbs oxidation and sulfuric acid cyclisation of the acid yielded 1-O-methyl-islandicin (174). 

Allylic nitro-compounds are alkylated with sodium diethyl malonate under catalysis by Pd to give predominantly the pyunsaturated malonates (153) in good yield (50—80 %) (Scheme 22). ... 

Our group reported that treatment of l-aryl-4,4,4-trifluorobutane-l,3-diones with PCI5 and then with sodium diethyl malonate afforded ethyl 4-aryl-6-(trifluoromethyl)-2-oxo-2/f-pyran-3-carboxylates (95) in moderate yields. These compounds can be converted in high yields to 2//-pyran-2-ones 96 by refluxing in aqueous acetic acid with H2SO4 [38]. Pyrones 95 and 96 react with sodium azide to produce highly functionalized (Z)-CF3-l,2,3-triazoles 97 and 98 [39a] (Scheme 29). 

The biosynthesis of chartreusin aglycone (74) in Streptomyces spp. has been investigated using trans-cinnamic acid, sodium diethyl malonate, and methionine as radioactive substrates. Preliminary results indicate that the complete carbon skeleton is derived by the acetate-polymalonate route. Since direct formation of (74) by cyclization of a p-polyketo-e ter intermediate is impossible, it has been suggested that a linear tetracyclic compound (73) could be involved as a biosynthetic intermediate (Scheme 14). 

---