di-tert-butyl ((2S,2'S)-(ethane-1,2-diylbis(azanediyl))bis(1-oxopropane-1,2-diyl))dicarbamate | 145414-41-1

• 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: di-tert-butyl ((2S,2'S)-(ethane-1,2-diylbis(azanediyl))bis(1-oxopropane-1,2-diyl))dicarbamate
• CAS: 145414-41-1
• 化学式: C₁₈H₃₄N₄O₆
• 分子量: 402.491
• InChiKey: QYYLSSJMXRVSPO-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  28.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  134.86
• 氢给体数：
  4.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  di-tert-butyl ((2S,2'S)-(ethane-1,2-diylbis(azanediyl))bis(1-oxopropane-1,2-diyl))dicarbamate 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-[2-[[(2S)-2-[(3-diphenylphosphanylbenzoyl)amino]propanoyl]amino]ethylamino]-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：

  N-叔丁氧羰基-L-丙氨酸 、 乙二胺 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61%的产率得到di-tert-butyl ((2S,2'S)-(ethane-1,2-diylbis(azanediyl))bis(1-oxopropane-1,2-diyl))dicarbamate
  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

• The Role of the Amino Acid-Derived Side Chain in the Preorganization of <i>C</i>₂-Symmetric Pseudopeptides: Effect on S_N2 Macrocyclization Reactions
  作者：Vicente Martí-Centelles、M. Isabel Burguete、Carlos Cativiela、Santiago V. Luis

  DOI：10.1021/jo4022309

  日期：2014.1.17

  of pseudopeptidic macrocycles containing non-natural amino acids have been synthesized. The macrocyclization reaction has been studied experimentally and computationally, demonstrating the key role of both the amino acid side chain and the catalytic bromide anion. The bromide anion acts as an external template assisting the folding of the open-chain precursor in a proper conformation. Computations revealed

  已经合成了包含非天然氨基酸的伪肽大环家族。已对大环化反应进行了实验和计算研究，证明了氨基酸侧链和催化溴化物阴离子均具有关键作用。溴化物阴离子充当外部模板，有助于以适当的构象折叠开链前体。计算表明，在阴离子的存在下，侧链对大环化能垒的影响很小。但是，对开链前体的构象平衡的影响非常重要。全面的，开链中间体的两个反应性末端以正确的方向彼此短距离定位的构象的稳定是决定大环化成功与否的关键参数。对于含环己基丙氨酸的化合物，发现了最佳收率，在存在溴的情况下，该化合物的计算预测最稳定的构象异构体–具有适当的预组织以进行环化。实验和理论之间取得的显着一致性表明，此处考虑的计算方法对于预测其他相关系统的行为以及设计通往新的大环化合物的适当合成路线可能具有很大的实用性。