(S)-2-(Benzhydrylidene-amino)-3-(5-benzyloxy-2-nitro-phenyl)-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one | 1026701-14-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-2-(Benzhydrylidene-amino)-3-(5-benzyloxy-2-nitro-phenyl)-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one
• 英文别名: (2S)-2-(benzhydrylideneamino)-1-[(1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3lambda6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]-3-(2-nitro-5-phenylmethoxyphenyl)propan-1-one；(2S)-2-(benzhydrylideneamino)-1-[(1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]-3-(2-nitro-5-phenylmethoxyphenyl)propan-1-one
• CAS: 1026701-14-3
• 化学式: C₃₉H₃₉N₃O₆S
• 分子量: 677.821
• InChiKey: ZXCGMDCBBDCBIU-DFTMULNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  49
• 可旋转键数：
  9
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  130
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (S)-2-(Benzhydrylidene-amino)-3-(5-benzyloxy-2-nitro-phenyl)-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one 在 lithium hydroxide 、 四丁基溴化铵 、 三乙胺 、 lithium bromide 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 3.0h， 生成 Boc-L-m-Nip(Bn)
  参考文献：
  名称：

  Design of New Photoactivatable Amino Acids: Stereoselective Synthesis of N-Protected Phenylalanine Derivatives as Precursors of p-Diazocyclohexadienone-Containing Peptides

  摘要：

  4-Diazocyclohexa-2,5-dienone-based amino acids m-Dip and o-Dip were designed for building up photoactivatable peptides. Their stable precursors L-3-[3-(benzyloxy)-6-nitrophenyl]alanine (L-m-Nip(Bn)) and L-3-[2-(benzyloxy)-5-nitrophenyl]alanine (L-o-Nip(Bn)) were synthesized by stereoselective alkylation of the corresponding benzyloxynitrobenzyl iodides by a chiral glycine equivalent. Alkylation was carried out using either butyllithium in dry organic solvents or a phase transfer procedure. Alkylation, hydrolysis of the adduct, and protection as Boc and Fmoc derivatives were achieved in 57-73% overall yields and led to 97-99% optically pure material. Boc or Fmoc-m/o-Nip(Bn) was inserted in model dipeptides Ac-mlo-Nip(Bn)-Ala-OMe or tripeptides Ala-Lm-Nip-(Bn)-Lys and Ala-L-o-Nip(Bn)-Arg, respectively, by homogeneous solution procedure and by solid-phase peptide synthesis. Deprotection and diazotization of the resulting p-hydroxyanilines gave the corresponding photoactivatable 4-diazocyclohexa-2,5-dienones containing peptides in quantitative yields. Such photoprobes are stable for several hours in the dark but are rapidly photolyzed at 350 nm or at 295 nm by a tryptophan-mediated energy transfer activation process.

  DOI：

  10.1021/jo00108a023
• 作为产物：
  描述：

  (5-(benzyloxy)-2-nitrophenyl)methanol 在 正丁基锂 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 丙酮 为溶剂， 反应 3.25h， 生成 (S)-2-(Benzhydrylidene-amino)-3-(5-benzyloxy-2-nitro-phenyl)-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one
  参考文献：
  名称：

  Design of New Photoactivatable Amino Acids: Stereoselective Synthesis of N-Protected Phenylalanine Derivatives as Precursors of p-Diazocyclohexadienone-Containing Peptides

  摘要：

  4-Diazocyclohexa-2,5-dienone-based amino acids m-Dip and o-Dip were designed for building up photoactivatable peptides. Their stable precursors L-3-[3-(benzyloxy)-6-nitrophenyl]alanine (L-m-Nip(Bn)) and L-3-[2-(benzyloxy)-5-nitrophenyl]alanine (L-o-Nip(Bn)) were synthesized by stereoselective alkylation of the corresponding benzyloxynitrobenzyl iodides by a chiral glycine equivalent. Alkylation was carried out using either butyllithium in dry organic solvents or a phase transfer procedure. Alkylation, hydrolysis of the adduct, and protection as Boc and Fmoc derivatives were achieved in 57-73% overall yields and led to 97-99% optically pure material. Boc or Fmoc-m/o-Nip(Bn) was inserted in model dipeptides Ac-mlo-Nip(Bn)-Ala-OMe or tripeptides Ala-Lm-Nip-(Bn)-Lys and Ala-L-o-Nip(Bn)-Arg, respectively, by homogeneous solution procedure and by solid-phase peptide synthesis. Deprotection and diazotization of the resulting p-hydroxyanilines gave the corresponding photoactivatable 4-diazocyclohexa-2,5-dienones containing peptides in quantitative yields. Such photoprobes are stable for several hours in the dark but are rapidly photolyzed at 350 nm or at 295 nm by a tryptophan-mediated energy transfer activation process.

  DOI：

  10.1021/jo00108a023

文献信息

• Design of New Photoactivatable Amino Acids: Stereoselective Synthesis of N-Protected Phenylalanine Derivatives as Precursors of p-Diazocyclohexadienone-Containing Peptides
  作者：C. Dugave

  DOI：10.1021/jo00108a023

  日期：1995.2

  4-Diazocyclohexa-2,5-dienone-based amino acids m-Dip and o-Dip were designed for building up photoactivatable peptides. Their stable precursors L-3-[3-(benzyloxy)-6-nitrophenyl]alanine (L-m-Nip(Bn)) and L-3-[2-(benzyloxy)-5-nitrophenyl]alanine (L-o-Nip(Bn)) were synthesized by stereoselective alkylation of the corresponding benzyloxynitrobenzyl iodides by a chiral glycine equivalent. Alkylation was carried out using either butyllithium in dry organic solvents or a phase transfer procedure. Alkylation, hydrolysis of the adduct, and protection as Boc and Fmoc derivatives were achieved in 57-73% overall yields and led to 97-99% optically pure material. Boc or Fmoc-m/o-Nip(Bn) was inserted in model dipeptides Ac-mlo-Nip(Bn)-Ala-OMe or tripeptides Ala-Lm-Nip-(Bn)-Lys and Ala-L-o-Nip(Bn)-Arg, respectively, by homogeneous solution procedure and by solid-phase peptide synthesis. Deprotection and diazotization of the resulting p-hydroxyanilines gave the corresponding photoactivatable 4-diazocyclohexa-2,5-dienones containing peptides in quantitative yields. Such photoprobes are stable for several hours in the dark but are rapidly photolyzed at 350 nm or at 295 nm by a tryptophan-mediated energy transfer activation process.