methyl (2S,3R)-2-[[(2S)-2-amino-2-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]acetyl]amino]-3-[tert-butyl(diphenyl)silyl]oxybutanoate | 260354-51-6

• 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: methyl (2S,3R)-2-[[(2S)-2-amino-2-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]acetyl]amino]-3-[tert-butyl(diphenyl)silyl]oxybutanoate
• CAS: 260354-51-6
• 化学式: C₃₅H₄₆N₂O₇Si
• 分子量: 634.845
• InChiKey: WJOOVFWGGVMVKA-ZHQYQSJASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  45
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  118
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  trans-4-(t-butyldiphenylsilyl)oxy-N-benzyloxycarbonyl-L-proline 、 methyl (2S,3R)-2-[[(2S)-2-amino-2-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]acetyl]amino]-3-[tert-butyl(diphenyl)silyl]oxybutanoate 在 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到benzyl (2S,4R)-4-[tert-butyl(diphenyl)silyl]oxy-2-[[(1S)-2-[[(2S,3R)-3-[tert-butyl(diphenyl)silyl]oxy-1-methoxy-1-oxobutan-2-yl]amino]-1-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-oxoethyl]carbamoyl]pyrrolidine-1-carboxylate
  参考文献：
  名称：

  A Strategy for the Asymmetric Aminohomologation of α,β-Dihydroxy Aldehydes:  Application to the Synthesis of the Southwest Tripeptide Segment of Echinocandin B

  摘要：

  The synthesis of the (2S,3S,4S)-3,4-dihydroxyhomotyrosine amino acid segment, present in echinocandin B, in its activated form ready for peptide coupling is described. The key steps of the approach are the enantioselective AD reaction of 4-methoxycinnamic acid methyl ester, a completely diastereoselective [2 + 2] hydroxyketene-imine cycloaddition, and the TEMPO-assisted cyclo-expansion of the resulting 3-hydroxy beta-lactam to the corresponding alpha-amino acid N-carboxy anhydride (NCA). The smooth opening of the latter upon treatment with L-Thr((OSiBuPh2)-Bu-t)OMe and further acylation with the N-Cbz protected L-4-tert-butyldiphenylsilyloxy proline rendered the southwest portion of echinocandin B.

  DOI：

  10.1021/jo990964c
• 作为产物：
  描述：

  [(2S,3R)-1-benzyl-2-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-oxoazetidin-3-yl] acetate 在 palladium on activated charcoal 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 lithium hydroxide 、 sodium hypochlorite 、 氢气 、 potassium bromide 作用下， 以 四氢呋喃 、 甲醇 、 phosphate buffer 、 二氯甲烷 、 水 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 44.0h， 生成 methyl (2S,3R)-2-[[(2S)-2-amino-2-[(4S,5S)-5-(4-methoxyphenyl)-2,2-dimethyl-1,3-dioxolan-4-yl]acetyl]amino]-3-[tert-butyl(diphenyl)silyl]oxybutanoate
  参考文献：
  名称：

  A Strategy for the Asymmetric Aminohomologation of α,β-Dihydroxy Aldehydes:  Application to the Synthesis of the Southwest Tripeptide Segment of Echinocandin B

  摘要：

  The synthesis of the (2S,3S,4S)-3,4-dihydroxyhomotyrosine amino acid segment, present in echinocandin B, in its activated form ready for peptide coupling is described. The key steps of the approach are the enantioselective AD reaction of 4-methoxycinnamic acid methyl ester, a completely diastereoselective [2 + 2] hydroxyketene-imine cycloaddition, and the TEMPO-assisted cyclo-expansion of the resulting 3-hydroxy beta-lactam to the corresponding alpha-amino acid N-carboxy anhydride (NCA). The smooth opening of the latter upon treatment with L-Thr((OSiBuPh2)-Bu-t)OMe and further acylation with the N-Cbz protected L-4-tert-butyldiphenylsilyloxy proline rendered the southwest portion of echinocandin B.

  DOI：

  10.1021/jo990964c

文献信息

• A Strategy for the Asymmetric Aminohomologation of α,β-Dihydroxy Aldehydes:  Application to the Synthesis of the Southwest Tripeptide Segment of Echinocandin B
  作者：Claudio Palomo、Mikel Oiarbide、Aitor Landa

  DOI：10.1021/jo990964c

  日期：2000.1.1

  The synthesis of the (2S,3S,4S)-3,4-dihydroxyhomotyrosine amino acid segment, present in echinocandin B, in its activated form ready for peptide coupling is described. The key steps of the approach are the enantioselective AD reaction of 4-methoxycinnamic acid methyl ester, a completely diastereoselective [2 + 2] hydroxyketene-imine cycloaddition, and the TEMPO-assisted cyclo-expansion of the resulting 3-hydroxy beta-lactam to the corresponding alpha-amino acid N-carboxy anhydride (NCA). The smooth opening of the latter upon treatment with L-Thr((OSiBuPh2)-Bu-t)OMe and further acylation with the N-Cbz protected L-4-tert-butyldiphenylsilyloxy proline rendered the southwest portion of echinocandin B.