67 β-ヒドロキシアミノ酸誘導体の触媒的不斉合成 : 光学活性金(1)錯体を触媒とするイソシアノ酢酸エステルとアルデヒドとの不斉アルドール反応

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Reaction of methyl isocyanoacetate with aldehydes (RCHO) in the presence of 1mol% of gold(I) catalyst prepared in situ by mixing bis(cyclohexyl isocyanide)gold(I) tetrafluoroborate and (R)-N-methyl-N-[2-(dialkylamino)ethyl]-1-[(S)-1',2-bis(diphenyl-phosphino)ferrocenyl]ethylamine in dichloromethane at 25℃ for 20-40h gave optically active 4-methoxycarbonyl-5-alkyl-2-oxazolines (1) with high enantio- and diastereoselectivity in a quantitative yield. The ratios of trans-1/cis-1 and enantiomeric purities of trans-1 are as follows: RCHO=PhCHO; 89/11, 96% ee (4S,5R). (E)-n-PrCH=CHCHO; 80/20, 87% ee. (E)-MeCH=CMeCHO; 91/9, 95% ee. MeCHO; 84/16, 72% ee (4S,5R). i-PrCHO; 98/2, 92% ee. c-HexCHO; 97/3, 90% ee. t-BuCHO; 100/0, 97% ee. The oxazolines 1 were converted readily into optically active β-hydroxyamino acids and their derivatives.
天然有機化合物討論会の論文
1986-09-09