Abstract
A very simple, safe and powerful method for the hydroxymethylation
of 2-bromoesters and lactones under anhydrous conditions that avoids
the use of gaseous formaldehyde is described. Moreover, under these
conditions, bromonitroalkanes were converted into the corresponding α-monohydroxymethylated
nitroalkanes, which are precursors of the corresponding α-amino
acids. Considering the easy transformation of ketones into bromonitroalkanes,
this represents a method for the formal synthesis of α-amino
acids from ketones.
Key words
hydroxymethylation - indium - esters - nitroalkanes - amino acids
References and Notes
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General Procedure :
To a suspension of indium powder (0.5 mmol) in THF (1 mL), the 2-bromocompound
(0.75 equiv) was added and the mixture was sonicated for 20 min. Paraformaldehyde
(0.5 mmol) was then added and sonication was continued for a further
4 h. The reaction mixture was quenched with sat. aq NaHCO3 (10
mL) and extracted with Et2 O (3 × 25 mL). The
combined organic layers were dried over MgSO4 , filtered
and the solvent was evaporated in vacuo to obtain pure hydroxymethylated compounds.
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