Dimethyl succinate synthesis

The asymmetric total synthesis of (+)-codeine, the unnatural enantiomer, was accomplished by J.D. White and coworkers using an intramolecular carbenoid insertion as the key step. The first stereogenic center that directed all subsequent stereochemical events was installed by the asymmetric hydrogenation of an alkylidene succinate that was obtained using the Stobbe condensation. Dimethyl succinate and isovanillin were reacted in the presence of excess sodium methoxide at reflux and the resulting reaction mixture was acidified to obtain the monomethyl ester. 

The phase separation of reactants hindered attempts to carry out lipase-catalyzed synthesis of poly(butylene succinate) (PBS) from succinic acid and 1,4-butanediol via dehydration. Therefore, in order to obtain a monophasic reaction mixture, dimethyl succinate was used in place of succinic acid. [49] The reaction mixture remained monophasic during the reaction course, and after 21 h at 95 °C PBS with M of 38000 was obtained. 

AI3-02480 Butanedioic acid, dimethyl ester CCRIS 4803 Dimethyl butanedioate Dimethyl succinate EINECS 203-419-9 FEMA No. 2396 HSDB 5370 Methyl butanedioate Methyl succinate NSC 52209 Succinic acid, dimethyl ester. Light and heat stabilizer for polyolefins, ABS polymer systems, flexible PVC, food packaging chemical intermediate. Liquid mp = 19° bp = 196.4° d = 1.0020 very soluble in Me2CO, CeHe, EtzO. Ashland Chemie Linz N. Am. DuPont Fluka Lancaster Synthesis Co. Penta Mfg. Sigma-Aldrich Fine Chem. 

Besides the aforementioned A-ring aromatic steroids and contraceptive agents, partial synthesis from steroid raw materials has also accounted for the vast majority of industrial-scale steroid synthesis. One notable exception, however, was the first industrial-scale synthesis of optically active steroids performed by workers at Roussel-UCLAF. The linear synthesis began with a suitable B—C-ring synfhon, 6-methoxy-l-tetralone (186). In a series of steps, tetralone (186) was converted to 2-methyl-2-cyanotetralone (270). Condensation of (270) with dimethyl succinate followed by carbonyl reduction, saponification, and resolution produced the optically active tricyclic acid (271). A series of reductions, a decarboxylation, and a hydrolysis produced (272). Appendage of the A-ring functionality by alkylation produced intermediate (273). Compound (273) was used as a common intermediate for the synthesis of 19-norsteroids, estrogens, and corticosteroids (230). 

Reaction of A-protected diethyl aspartate (130) or glutamate (131) with lithium trialkylphosphonoacetate in the presence of DIBALH leads to selective formation of the A-protected y-amino-a,P-unsaturated dicarboxylates (132) as the major product. 3-(Phosphonomethyl)cyclo-pentenones (133) and -hexenones (134) are the products of the reaction of dimethyl succinate and dimethyl glutarate, respectively, with excess dimethyl (lithiomethyl)phosphonate presumably via two phosphonomethylations followed by an intramolecular olefmation. Examples of the many phosphonate olefmation reactions carried out include the synthesis of (2E, 4Z)-4-aminoalkadienoates (135), 2-aryloxy-3-phenylpropenoates (136), and isoxazoles (137). ... 

This was followed shortly by a stereo- and enantiocontrolled synthesis of (—)-chimonanthine (154) and calycanthine (150) as well as a second route to meso-chimonanthine (152). The central step in this synthesis features the use of a double Heck cyclization to create vicinal quaternary carbon centers in high yields and with complete stereocontrol 124). The synthesis commenced with a double alkylation of the lithium dienolate of dimethyl succinate 194 and tartrate-derived diiodide 195 to give a diastereomeric mixture of the saturated diesters. Subsequent oxidation of the diesters, followed in succession by aminolysis, A-benzylation, removal of the benzyl ethers, and silylation, provided the cyclization substrate 197, which on Heck cyclization yielded a single product, 198, a pentacyclic bisoxindole, subsequently shown to have the meso relationship of the two oxindole groups. Further manipulations of 198 led eventually to the diazide derivative 199, which can be processed to we.so-chimonanthine (152), following the procedure established in the preceding synthesis (Scheme 14). 

Azim and co-workers [29] described the CALB-catalysed synthesis of polybutylene succinate (PBS) via condensation polymerisation nsing a monophasic reaction mixture of dimethyl succinate and 1,4-BDO in bulk and in solution. 

Sodium toluene dispersion of, 55, 65 Sodium p-toluenesulfinate, 57, 103 Spiro[4 n] alkenones, 58, 62 Spiro[cyclopentane-l,l -indene] 55, 94 Squalene, 56, 116 Squalene, 2,3-epoxy, 56, 116 Stannic chloride, 56, 97 Steroids synthesis, 58, 85 E Stilbene, 55, 115,58, 73 z-Stilbene, 58, 133 Styrene, 56, 35,58, 43 Styrene glycol, 55, 116 Styrene glycol dimesylate, 55, 116 Succinic acid, 58, 85 Succinic anhydride, 58, 85 Sucunimide, 56, 50, 58, 126 Succimmide, Vbromo, 55, 28, 56, 49 SULFIDE CONTRACTION, 55, 127 Sulfide, dimethyl-, 56, 37 SULFIDE SYNTHESIS, 58, 143,58, 138 SULFIDE SYNTHESIS ALKYL ARYL SULFIDES, 58, 143 SULFIDE SYNTHFSIS DIALKYL SULFIDES, 58, 143 SULFIDE SYNTHESIS UNSYMMETRI-CAL DIALKYL DISULFIDES, 58, 147 SULFONYL CYANIDES, 57, 88 Sulfur tetrafluoride, 57, 51... 

Synthesis of bis(pyrrole) monomers. The condensation of ethyl diacetyl succinate with amines to give dialkyl esters of N substituted pyrroles proceeds in near quantitative yields to the bis(dicarboethoxy dimethyl pyrrole). 

The diester 87 with the same tetracyclic skeleton as 83 had previously been prepared by Paquette et al. via a domino Diels-Alder reaction of 5,5 -bicyclo-pentadienyl 84 with dimethyl acetylenedicarboxylate (Scheme 20) [73]. The key precursor 84 was obtained by iodine-induced oxidative coupling of the copper cyclopentadienide derived from the sodium derivative. The diester 85 formed along with 86 was transformed into a bissilyl bisenol ether by reductive cleavage of the central bond in the succinate moiety with sodium in the presence of trimethylsilyl chloride. Subsequent hydrolysis of the bisenol ether - actually a bisketene acetal - gave the dienic tetraquinacenedicarboxylate 87. This compound served as the key intermediate in the first synthesis of dodecahedrane 88 [74]. 

---