1-[N-(9-fluorenylmethyloxycarbonyl)-(1S)-1-amino-2-oxobutyl]-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane | 206191-08-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1-[N-(9-fluorenylmethyloxycarbonyl)-(1S)-1-amino-2-oxobutyl]-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane
• 英文别名: 9H-fluoren-9-ylmethyl N-[(1S)-1-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)-2-oxobutyl]carbamate
• CAS: 206191-08-4
• 化学式: C₂₅H₂₇NO₆
• 分子量: 437.492
• InChiKey: VMBMNLIWYQMFKU-BSSNWTCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-[N-(9-fluorenylmethyloxycarbonyl)-(1S)-1-amino-2-oxobutyl]-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane 在 锂硼氢 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 9H-fluoren-9-ylmethyl N-[(1S,2R)-2-hydroxy-1-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)butyl]carbamate 、 9H-fluoren-9-ylmethyl N-[(1S,2S)-2-hydroxy-1-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)butyl]carbamate
  参考文献：
  名称：

  Stereoselective Synthesis of Threo and Erythro β-Hydroxy and β-Disubstituted-β-Hydroxy α-Amino Acids

  摘要：

  Optically pure N-protected serine aldehyde equivalents can be prepared by the protection of the carboxylic group of serine by a cyclic ortho ester. Alkylation of N-Cbz-, N-Fmoc- or N-Boc-protected serine with oxetane tosylate 1 or bromide 2 gives the corresponding oxetane esters 4a-c which can easily be converted to the cyclic ortho esters 5a-c. A variety of unusual threo beta-hydroxy amino acids have been synthesized by Grignard addition to these optically pure serine aldehyde equivalents. The erythro diastereomers can be obtained by oxidation of the initial three adduct followed by reduction with LiBH4. Also described is a general approach for the diastereoselective synthesis of optically pure beta,beta-dialkyl-beta-hydroxy alpha-amino acids. These highly substituted amino acids are prepared by a sequence of Grignard addition to the optically active serine aldehyde equivalent, followed by oxidation of the initial adduct, and a second Grignard addition to the resulting ketone. The hydroxy adduct is obtained with very high diastereoselectivity (84-96% de). All four diastereomers can be selectively synthesized by varying the order of the Grignard additions and the chirality of the initial synthon. Removal of the protecting groups can be effected in very mild conditions, giving excellent yields of highly substituted amino acids in high diastereomeric purity.

  DOI：

  10.1021/jo972294l
• 作为产物：
  描述：

  在 草酰氯 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 生成 1-[N-(9-fluorenylmethyloxycarbonyl)-(1S)-1-amino-2-oxobutyl]-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane
  参考文献：
  名称：

  Stereoselective Synthesis of Threo and Erythro β-Hydroxy and β-Disubstituted-β-Hydroxy α-Amino Acids

  摘要：

  Optically pure N-protected serine aldehyde equivalents can be prepared by the protection of the carboxylic group of serine by a cyclic ortho ester. Alkylation of N-Cbz-, N-Fmoc- or N-Boc-protected serine with oxetane tosylate 1 or bromide 2 gives the corresponding oxetane esters 4a-c which can easily be converted to the cyclic ortho esters 5a-c. A variety of unusual threo beta-hydroxy amino acids have been synthesized by Grignard addition to these optically pure serine aldehyde equivalents. The erythro diastereomers can be obtained by oxidation of the initial three adduct followed by reduction with LiBH4. Also described is a general approach for the diastereoselective synthesis of optically pure beta,beta-dialkyl-beta-hydroxy alpha-amino acids. These highly substituted amino acids are prepared by a sequence of Grignard addition to the optically active serine aldehyde equivalent, followed by oxidation of the initial adduct, and a second Grignard addition to the resulting ketone. The hydroxy adduct is obtained with very high diastereoselectivity (84-96% de). All four diastereomers can be selectively synthesized by varying the order of the Grignard additions and the chirality of the initial synthon. Removal of the protecting groups can be effected in very mild conditions, giving excellent yields of highly substituted amino acids in high diastereomeric purity.

  DOI：

  10.1021/jo972294l