Syntheses from Vinylene Carbonate

The ability of furan to undergo both the forward and reverse Diels-Alder reaction has been used to synthesize 1,3-dioxoles, and the reaction appears to have wide applicability. In Scheme 42 the synthesis of 2-phenyl-l,3-dioxole is shown. The key to the process is the dialcohol (119), which is obtained from vinylene carbonate as shown. The dialcohol (119) has the potential of serving as an intermediate for a variety of 2-substituted 1,3-dioxolanes (73JA7161). 

The classical diene synthesis has been used for building the six-membered ring in the preparation of a/to-inositol by Criegee and Becher.36 trans, trans-Diacetoxybutadiene (XVI) and vinylene carbonate (XVII) condensed at 205-210° to an addition product (XVIII). Hydroxylation of this compound by osmium tetroxide, followed by hydrolysis, gave aWo-inositol the bulky osmium tetroxide approaches from the unhindered side of the molecule and the other possible product of the hydroxylation, m-inositol, is not formed.4 trans-Hydroxy 1 ation of XVIII would give epi-inositol. 

Several new variations of methods for preparation of indoles by Pd-mediated cyclization were reported. Vinylene carbonate was found to be a satisfactory C2-C3 precursor for synthesis of N-acylindolin-2-ols and A-acylindoles from o-iodoacetanilides under Heck conditions. <95H(41)1627>... 

Periodate cleavage of an oxabicyclic diol was also a key step in the synthesis of citreoviral from the Diels-Alder adduct of 2,4-dimethylfuran and vinylene carbonate [136]. 

Bulk polymerization of vinylene carbonate (VCA) initiated by 60Co y-rays was studied at 30°-110°C at a constant dose rate of 1 - 105 rad/hr. An overall activation energy of 5.0 kcal/mole and a maximum reaction rate of 1 10 3 mole/l-sec were obtained. As has been reported, purification of the monomer is a crucial point because inhibiting impurities are formed during the synthesis. From experiments with chlorine-substituted ethylene and vinylene carbonates, we tentatively conclude that, in addition to mono- and dichloroethylene carbonate, dichloro-vinylene carbonate is mainly responsible for the inhibition. The copolymerization behavior of VC A with some chlorine-substituted olefins was studied. Chlorotrifluoroethylene (CTFE) is an especially suitable comonomer the reactivity ratios found were rVCA = 0.42 and rCXFE = 0.48. 

Field and Schaefgen (5) demonstrated that a high molecular weight poly (vinylene carbonate) (PVCA) was obtained if the first step of the synthesis, photochlorination of ethylene carbonate, was carried out in CC14 instead of bulk reaction and if the monomer was distilled from NaBH4 shortly before polymerization. On the other hand, bulk chlorination led invariably to poor quality VCA. 

The dienophilic properties of vinylene carbonate (1,3-dioxol-2-one, 6) have been repeatedly exploited for the synthesis of cyclic polyols. Recently a number of ribofuranose derivatives have been synthesized starting from 6. The known adduct 7, obtained from 6 and furan, was c/r-hydroxylated, and after acetonation was hydrolyzed with base and cleaved with permanganate to give the dicarboxylic acid 8. The corresponding anhydride 9 gave, on treatment with trimethylsilyl azide, the isocyanate 10, which in turn was converted into the carbonate 11 on addition of methanol. The monoester 12, obtained in the reaction of anhydride 9 with isopropanol, was effectively resolved into enantiomers by the use of brucine or (/ )-l-(2-naphthyl)ethylamine. ... 

A -methylpyrrolidine to a number of ketones. When these intermediates are generated in the presence of (57 )-5-menthyloxyfuran-2[5il/]-one addition takes place to the double bond of the furanone. The adducts obtained from the addition of vinylene carbonate to such homochiral furanones have been used in a new stereoselective synthesis of butyrolactones of lyxofuranose. ... 

The monodilorinated vinylene carbonate is also used in the synthesis of Cefcand, a new cephalosporin from Kyoto and Astra [112, 113]. 

The synthesis of the 2,5-disubstituted pyrrolidine 43 from D-mannitol by standard chemistry and the synthesis of pyrrolidines 44 by addition of azomethine ylides to vinylene carbonate " as well as the synthesis of the imino-heptitol 45 from 2,3 5,6-di-0-isopropylidene-a-D-mannofuranose have been reported. 

A soln. of benz[a]anthracene in 10 moles vinylene carbonate refluxed 18 hrs. under Ng at ca. 175-180° 7,12-dihydro-7,12-ethanobenz[a]anthracene-13,14-diol cyclic carbonate. Y 80%.-This is the first step of a high-yield multi-step synthesis of 7,12-dimethylbenz[a]anthracenes from benz[a]anthracenes. F. e. s. M. S. Newman and Zia Ud Din, J. Org. Chem. 36, 966 (1971) diene synthesis with anthracenes s. a. D. M. McKinnon and J. Y. Wong, Can. J. Chem. 49, 3178 (1971) synthesis of dibenzobarrelenes s. H. P. Figeys and A. Dralantis, Tetrahedron 28, 3031 (1972). 

Baran, A., Kazaz, C., Se9en, H., Sutbeyaz, Y. 2003. Synthesis of haloconduiitols from an endo-cycload-duct of furan and vinylene carbonate. Tetrahedron 59 3643-3648. 

The cleavage of oxetans formed in the Paterno-Biichi reaction has also been used with effect.Thus an extremely simple and efficient synthesis of D,L-apiose (53) involved the base-induced cleavage of the oxetan (52), derived from diacetoxyacetone and vinylene carbonate (Scheme 15). A reductive cleavage of... 

A total synthesis of ( )-citreoviral (392), a metabolite of Penicillium citreoviride B, starting from 2,4-dimethylfuran and vinylene carbonate was reported by Yamamura and coworkers [139]. The reaction produced a 7 5 mixture of the exolendo-cyclozAducts 388 in 65% combined yield. From 388, the synthesis of ( )-citreoviral 392 required 19 steps (Scheme 13.83). 

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