2,2,2-trichloroethyl (2S)-2-[(tert-butoxycarbonyl)amino]-4-(2,2-dimethyl-4,6-dioxo-1,3-dioxolan-5-yl)butanoate | 480460-69-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,2,2-trichloroethyl (2S)-2-[(tert-butoxycarbonyl)amino]-4-(2,2-dimethyl-4,6-dioxo-1,3-dioxolan-5-yl)butanoate
• 英文别名: 2,2,2-trichloroethyl (2S)-4-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoate
• CAS: 480460-69-3
• 化学式: C₁₇H₂₄Cl₃NO₈
• 分子量: 476.738
• InChiKey: ZKHJCRABLZBTST-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  117
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,2,2-trichloroethyl (2S)-2-[(tert-butoxycarbonyl)amino]-4-(2,2-dimethyl-4,6-dioxo-1,3-dioxolan-5-yl)butanoate 以 甲苯 为溶剂， 以42%的产率得到2-(2,2,2-trichloroethyl) 1-tert-butyl (2S)-6-oxo-1,2-piperidinedicarboxylate
  参考文献：
  名称：

  Diastereoselective Hydroxylation of 6-Substituted Piperidin-2-ones. An Efficient Synthesis of (2S,5R)-5-Hydroxylysine and Related α-Amino Acids

  摘要：

  The synthesis of (2S,5R)-5-hydroxy-6-oxo-1,2-piperidinedicarboxylates (5) and related (3S,W-3hydroxy-6-alkyl-2-oxo-1-piperidinecarboxylates has been developed. The approach is based on the asymmetric hydroxylation of enolates generated from the corresponding N-protected-6-substituted piperidin-2-ones. The utility of 5a as a precursor in the synthesis of (2S,5R)-5-hydroxylysine (1), an amino acid unique to collagen and collagen-like proteins, has also been demonstrated. (2S)-6oxo-1,2-piperidinedicarboxylates (6) required for hydroxylation studies were prepared in 38-74% yield, starting from conveniently protected aspartic acid as inexpensive chiral adduct. Hydroxylation of 6 to 5 proceeds in high yield and excellent diastereoselectivity by treatment of their Li-enolate with (+)-camphorsulfonyloxaziridine at -78 degreesC. Ring opening of di-tert-butyl (2S,5R)-6-oxo-1,2-piperidinedicarboxylate ((5R)-5a) under reductive conditions afforded the corresponding 1,2-diol (17) in 91%, which was further transformed to (2S,5R)-5-hydroxylysine in four steps (84%). 17 is also a versatile intermediate in the preparation of tert-butyl (2S,M)-2-[(tert-butoxycarbonyl)aminol 5-hydroxy-6-iodohexanoate (3) and tert-butyl (2S)-2-[(tert-butoxycarbonyl)aminol-4-[(2,R)-oxiranyl]- butanoate (4), two amino acid derivatives used in the total synthesis of the bone collagen cross-link (+)-pyridinoline (2a).

  DOI：

  10.1021/jo025950c
• 作为产物：
  描述：

  (S)-2-tert-Butoxycarbonylamino-4-(2,2-dimethyl-4,6-dioxo-[1,3]dioxan-5-yl)-4-oxo-butyric acid 2,2,2-trichloro-ethyl ester 在 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以3.66 g的产率得到2,2,2-trichloroethyl (2S)-2-[(tert-butoxycarbonyl)amino]-4-(2,2-dimethyl-4,6-dioxo-1,3-dioxolan-5-yl)butanoate
  参考文献：
  名称：

  Diastereoselective Hydroxylation of 6-Substituted Piperidin-2-ones. An Efficient Synthesis of (2S,5R)-5-Hydroxylysine and Related α-Amino Acids

  摘要：

  The synthesis of (2S,5R)-5-hydroxy-6-oxo-1,2-piperidinedicarboxylates (5) and related (3S,W-3hydroxy-6-alkyl-2-oxo-1-piperidinecarboxylates has been developed. The approach is based on the asymmetric hydroxylation of enolates generated from the corresponding N-protected-6-substituted piperidin-2-ones. The utility of 5a as a precursor in the synthesis of (2S,5R)-5-hydroxylysine (1), an amino acid unique to collagen and collagen-like proteins, has also been demonstrated. (2S)-6oxo-1,2-piperidinedicarboxylates (6) required for hydroxylation studies were prepared in 38-74% yield, starting from conveniently protected aspartic acid as inexpensive chiral adduct. Hydroxylation of 6 to 5 proceeds in high yield and excellent diastereoselectivity by treatment of their Li-enolate with (+)-camphorsulfonyloxaziridine at -78 degreesC. Ring opening of di-tert-butyl (2S,5R)-6-oxo-1,2-piperidinedicarboxylate ((5R)-5a) under reductive conditions afforded the corresponding 1,2-diol (17) in 91%, which was further transformed to (2S,5R)-5-hydroxylysine in four steps (84%). 17 is also a versatile intermediate in the preparation of tert-butyl (2S,M)-2-[(tert-butoxycarbonyl)aminol 5-hydroxy-6-iodohexanoate (3) and tert-butyl (2S)-2-[(tert-butoxycarbonyl)aminol-4-[(2,R)-oxiranyl]- butanoate (4), two amino acid derivatives used in the total synthesis of the bone collagen cross-link (+)-pyridinoline (2a).

  DOI：

  10.1021/jo025950c