{(S)-1-[6-((S)-2-tert-Butoxycarbonylamino-propionylamino)-hexylcarbamoyl]-ethyl}-carbamic acid tert-butyl ester | 906747-78-2

• 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: {(S)-1-[6-((S)-2-tert-Butoxycarbonylamino-propionylamino)-hexylcarbamoyl]-ethyl}-carbamic acid tert-butyl ester
• 英文别名: tert-butyl N-[(2S)-1-[6-[[(2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoyl]amino]hexylamino]-1-oxopropan-2-yl]carbamate
• CAS: 906747-78-2
• 化学式: C₂₂H₄₂N₄O₆
• 分子量: 458.599
• InChiKey: GCCNOUYCZSBKJA-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  135
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  {(S)-1-[6-((S)-2-tert-Butoxycarbonylamino-propionylamino)-hexylcarbamoyl]-ethyl}-carbamic acid tert-butyl ester 在 1-羟基苯并三唑 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 3-diphenylphosphanyl-N-[(2S)-1-[6-[[(2S)-2-[(3-diphenylphosphanylbenzoyl)amino]propanoyl]amino]hexylamino]-1-oxopropan-2-yl]benzamide
  参考文献：
  名称：

  “Backdoor Induction” of Chirality: Asymmetric Hydrogenation with Rhodium(I) Complexes of Triphenylphosphane-Substituted β-Turn Mimetics

  摘要：

  Bioconjugate bidentate ligands 2-10 were obtained by tethering triphenylphosphanecarboxylic acid to amino acid substituted spacers with different flexibility, ranging from a rigid enediyne-based beta-turn inducer to flexible linear aliphatic chains with up to eight carbon atoms. The 21 synthesized ligands revealed up to 81% ee selectivity in rhodium-catalyzed asymmetric hydrogenation of alpha,beta-unsaturated amino acids. The key feature of the catalysts is the prochiral coordination sphere of the catalytic metal while the chirality is transmitted by "backdoor induction" from distant hydrogen-bonded amino acids. DFT calculations were applied to study the structure and relative stability of the precatalytic organometallic Rh(I) complexes, with particular emphasis on hydrogen-bonded secondary structures.

  DOI：

  10.1021/om5005385
• 作为产物：
  描述：

  1,6-己二胺 、 N-叔丁氧羰基-L-丙氨酸 在 1-羟基苯并三唑 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以86%的产率得到{(S)-1-[6-((S)-2-tert-Butoxycarbonylamino-propionylamino)-hexylcarbamoyl]-ethyl}-carbamic acid tert-butyl ester
  参考文献：
  名称：

  “Backdoor Induction” of Chirality: Asymmetric Hydrogenation with Rhodium(I) Complexes of Triphenylphosphane-Substituted β-Turn Mimetics

  摘要：

  Bioconjugate bidentate ligands 2-10 were obtained by tethering triphenylphosphanecarboxylic acid to amino acid substituted spacers with different flexibility, ranging from a rigid enediyne-based beta-turn inducer to flexible linear aliphatic chains with up to eight carbon atoms. The 21 synthesized ligands revealed up to 81% ee selectivity in rhodium-catalyzed asymmetric hydrogenation of alpha,beta-unsaturated amino acids. The key feature of the catalysts is the prochiral coordination sphere of the catalytic metal while the chirality is transmitted by "backdoor induction" from distant hydrogen-bonded amino acids. DFT calculations were applied to study the structure and relative stability of the precatalytic organometallic Rh(I) complexes, with particular emphasis on hydrogen-bonded secondary structures.

  DOI：

  10.1021/om5005385

文献信息

• Synthesis and Solid-State Secondary Structure Investigation of Silk−Proteinlike Multiblock Polymers
  作者：Jinrong Yao、Dahui Xiao、Xin Chen、Ping Zhou、Tongyin Yu、Zhengzhong Shao

  DOI：10.1021/ma034573i

  日期：2003.10.1

  measurements revealed the oligopeptide segments in these multiblock polymers could aggregate spontaneously into β-sheet structure in solid state. In addition, it was also found there were non-β-sheet structures in the synthetic polymers, which indicated such polymers had a solid-state structure similar to that of natural silks.

  与双（寡肽）和二异氰酸酯，二丝proteinlike多嵌段聚合物（的逐步增长聚合P1，P2），含- （ALA）4 -和- （GlyAlaGlyAla） -序列从蜘蛛拖丝的结晶区域导出并蚕（Bombyx mori）蚕丝分别已成功合成。在25°C的二氯乙酸中测得的P1和P2的特性粘度分别为0.31和0.26 dL / g。红外，13C CP / MAS NMR和WAXD测量表明，这些多嵌段聚合物中的寡肽链段可以自发聚集成固态的β-折叠结构。另外，还发现合成聚合物中存在非β-折叠结构，这表明这种聚合物具有类似于天然丝的固态结构。
• “Backdoor Induction” of Chirality: Asymmetric Hydrogenation with Rhodium(I) Complexes of Triphenylphosphane-Substituted β-Turn Mimetics
  作者：Zoran Kokan、Zoran Glasovac、Maja Majerić Elenkov、Matija Gredičak、Ivanka Jerić、Srećko I. Kirin

  DOI：10.1021/om5005385

  日期：2014.8.11

  Bioconjugate bidentate ligands 2-10 were obtained by tethering triphenylphosphanecarboxylic acid to amino acid substituted spacers with different flexibility, ranging from a rigid enediyne-based beta-turn inducer to flexible linear aliphatic chains with up to eight carbon atoms. The 21 synthesized ligands revealed up to 81% ee selectivity in rhodium-catalyzed asymmetric hydrogenation of alpha,beta-unsaturated amino acids. The key feature of the catalysts is the prochiral coordination sphere of the catalytic metal while the chirality is transmitted by "backdoor induction" from distant hydrogen-bonded amino acids. DFT calculations were applied to study the structure and relative stability of the precatalytic organometallic Rh(I) complexes, with particular emphasis on hydrogen-bonded secondary structures.