Methoxymethyl diazomethane

Methoxymethyl aryl ethers, Ar0CH20CH3. These ethers can be prepared by treatment of phenols with NaH in ether-DMF followed by chloromethyl methyl ether. Ronald reports that these ethers show enhanced susceptibility at the orfho-position to halogen-metal exchange, particularly with f-butyllith-ium. Thus (1) can be converted into (2) in high yield by metalation, reaction with CO2, and then reaction with diazomethane. In contrast, the methyl ether of OT-cresol under similar conditions gives less than 1% yield of carboxylic acids. 

Steroidal methyl ethers are readily obtained from the alcohols with diazomethane and fluoroboric acid. The novel dicholesteryl acetal (132) of formaldehyde has been obtained from cholesterol, either by the anodic oxidation of a solution in aqueous acidic methanol, or by the action of sodium hydride and chloromethyl methyl ether. Dimethoxymethane undergoes partial exchange with cholesterol in acidic solution to give the methoxymethyl ether (133). ... 

Weakly acidic phenols that do not react with diazomethane can be methylated with sodium hydride and methyl iodide in THF at room temperature. The methoxymethyl ether moiety can be used to protect phenols. It is stable to alkali, Grignard reagents, lithium aluminum hydride, and catalytic hydrogenation, and is readily removed by mineral acid. Dimethoxymethane can be used in lieu of the carcinogenic chloromethyl methyl ether for this purpose. Alternatively, phenols may be protected as methyl thiomethyl ethers.The (9-acetylation of phenols in the presence of primary and secondary amines can be carried out with acetyl bromide and TFA. ... 

Chiral 2-amino-1,3-dienes with (5)-2-methoxymethyl pyrrolidine substituents react with vinyl carbene complexes, [(OC)5W=C(OMe)C(R3)=C(R )(R5)] to give the cyclohexyl tungsten carbene complexes S6. 27 Cyclic carbenes 57 (R = H, Br, OMe) and 58 are rather unreactive towards 1,3-dipoles and 1,3-dienes and their reactions with diazomethane are regio- but not chemoselective. s The tungsten atom of 59 has distorted octahedral coordination defined by one carbene and five carbonyl ligands. ... 

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