Methyl methoxymagnesium carbonate

Finkbeiner408 has described the alkylation of hydantoins on the way to a synthesis of amino acids. The methylene group is first activated by introducing an alkoxycarbonyl group by means of methoxymagnesium methyl carbonate then the amino acid is obtained by alkylation and subsequent hydrolysis with decarboxylation. The original paper should be consulted for details. 

The reaction of nitroalkanes with methoxymagnesium methyl carbonate represents an acylation by carbonic acid it affords good yields of <%-nitro carboxylic acids by way of a chelate-like intermediate 433... 

Methoxymagnesium methyl carbonate N-Condensed zl -pyrroline ring... 

Startg. keto lactam added to methoxymagnesium methyl carbonate in methanol, and refluxed 48 hrs. product. Y 71%. S. Danishefsky, T. A. Bryson, and J. Puthenpurayil, J. Org. Chem. 40, 1846 (1975). 

Magnesium methyl carbonate (Methyl methoxymagnesium carbonate)... 

Methanol, heated at 250°C with chloroform or carbon tetrachloride in contact with active carbon, is converted in part to methyl chloride (52). Methyl chloride has been produced from methoxymagnesium chloride, CH OMgCl, a by-product from the manufacture of certain organo—sHicon compounds, by heating over 200°C (53). 

Acrylic monomers can be derived from biomass (53). An early synthesis of a-methylene-y-valerolactone involves two steps (54,55). The first step is the carboxylation of y-butyrolactone with methyl methoxymagnesium carbonate Stiles reagent) to produce the acid. Next, the acid is briefly treated with a mixture of aqueous formaldehyde and diethylamine, followed by a separate treatment of the crude product with sodium acetate in acetic acid. The first step requires 6-7 h and affords almost quantitative yields, whereas the second step can be accomplished in less than 30 min but with yields of only 50%. 

Scheme 29. Synthesis of racemic protolichesterinic acid by carboxylation of y-butyrolactones with methyl methoxymagnesium carbonate...

Martin J, Watts PC, Johnson F (1974) Carboxylations of y-Butyrolactones with Methyl Methoxymagnesium Carbonate. A New Synthesis of dl-Protolichesterinic Acid. J Org Chem 39 1676. 

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