Enantiospecific alkylations of alanine

摘要

Reaction of ferrocenecarbaldehyde 3 with sodium (S)-alaninate followed by pivaloyl chloride generates (2S,4S)-2-ferrocenyl-3-pivaloyl-4-methyl-1,3-oxazolidin-5-one 5 (>98% de), Compound 5 undergoes stereospecific 4-alkylation with complete retention of configuration on treatment sequentially with lithium diisopropylamide and an appropriate alkyl bromide (benzyl bromide, allyl bromide, crotyl [(E)-but-2-enyl] bromide, alpha-bromo-o-xylene, cinnamyl bromide, 2-(bromomethyl)naphthalene, 1-(tert-butoxycarbonyl)-3-(bromomethyl)indole and bromoacetonitrile} to generate the corresponding (2S,4R)-2-ferrocenyl-3-pivaloyl-4-alkyl-4-methyl-1,3-oxazolidin-5-ones 7a-h. Hydrolysis of (2S,4R)-7a-h on Amberlyst-15 generates the free (R)-alpha-methyl-alpha-amino acids (R)-8a-h. [References: 65]