[(S)-1-((R)-2-hydroxy-1-phenyl-ethylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester | 443681-10-5

• 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-((R)-2-hydroxy-1-phenyl-ethylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester
• 英文别名: tert-butyl N-[(1S)-1-({[(1R)-2-hydroxy-1-phenylethyl]amino}carbonyl)-2-methylpropyl]carbamate；tert-butyl 1-(2-hydroxy-1-phenylethylamino)-3-methyl-1-oxobutan-2-yl carbamate；tert-butyl N-[(2S)-1-[[(1R)-2-hydroxy-1-phenylethyl]amino]-3-methyl-1-oxobutan-2-yl]carbamate
• CAS: 443681-10-5
• 化学式: C₁₈H₂₈N₂O₄
• 分子量: 336.431
• InChiKey: HPWMDECGGBAKGS-GJZGRUSLSA-N

物化性质

• 熔点：
  153-154 °C(Solv: dichloromethane (75-09-2); pentane (109-66-0))
• 沸点：
  539.1±50.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  87.7
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(S)-1-((R)-2-hydroxy-1-phenyl-ethylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以98%的产率得到N-1-[(1R)-2-hydroxy-1-phenylethyl]-(2S)-2-amino-3-methylbutanamide
  参考文献：
  名称：

  利用自然界的结构多样性：开发用于钌催化的酮的对映选择性转移氢化的模块化二肽类似物配体。

  摘要：

  基于叔丁氧羰基（N-Boc）-保护的α-氨基酸和手性邻位氨基醇的组合，制备了新颖的二肽-类似物配体的文库。这些高度模块化的配体与[[RuCl（2）（p-cymene）]（2）]结合，并筛选得到的金属配合物作为催化剂，用于在转移氢化条件下使用2-丙醇作为氢供体的对苯乙酮对映选择性还原。用几种新颖的催化剂可获得极好的1-苯基乙醇对映体选择性（ee高达98％）。尽管大多数配体包含两个立体中心，但已证明产物醇的绝对构型是由配体的氨基酸部分的构型决定的。利用基于L-氨基酸的配体生成S-构型产物，基于D-氨基酸的催化剂有利于R-构型醇的形成。N-Boc-L-丙氨酸和（R）-苯基甘醇（Boc-L-Ab）或其对映异构体（N-Boc-D-丙氨酸和（S）-苯基甘醇，Boc-D-Aa）的组合被证明是还原过程的最佳配体。评估了许多芳基烷基酮的转移氢化反应，并获得了极佳的对映选择性，最高可达96％ee。

  DOI：

  10.1002/chem.200304900
• 作为产物：
  描述：

  (1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-phenylethanamine 在 四丁基氟化铵 、 1-羟基苯并三唑 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 36.0h， 生成 [(S)-1-((R)-2-hydroxy-1-phenyl-ethylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester
  参考文献：
  名称：

  Asymmetric transfer hydrogenation using amino acid derivatives; further studies and a mechanistic proposal

  摘要：

  A series of investigations into the use of amino acid derivatives for the asymmetric catalysis of the transfer hydrogenation of ketones are presented. Based on the results observed, a mechanistic suggestion for the origin of the ellantioselective induction is proposed. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.004
• 作为试剂：
  描述：

  4-溴苯乙酮 在 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ sodium hydroxide 、 异丙醇 、 [(S)-1-((R)-2-hydroxy-1-phenyl-ethylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester 作用下， 反应 2.0h， 生成 1-(4-溴苯基)-1-乙醇
  参考文献：
  名称：

  新型简单且高度模块化的配体，可有效地实现酮的不对称转移加氢。

  摘要：

  新型简单和高度模块化的二肽类似物配体与[RuCl2（p-cymene）] 2结合，可在氢转移条件下以高达96％的对映选择性有效催化酮的还原。

  DOI：

  10.1039/b206471e

文献信息

• Rhodium-Catalyzed Asymmetric Transfer Hydrogenation of Aryl Alkyl Ketones Employing Ligands Derived from Amino Acids
  作者：Jenny Wettergren、Alexey B. Zaitsev、Hans Adolfsson

  DOI：10.1002/adsc.200700345

  日期：2007.12.10

  The combination of (pentamethylcyclopentadienyl)rhodium dichloride dimer [RhCl2Cp*}2] and pseudodipeptide ligands, formed from N-Boc protected amino acids and amino alcohols, resulted in efficient and selective catalysts for the asymmetric transfer hydrogenation of ketones in 2-propanol. A number of different secondary alcohols was obtained in high yields and in excellent enantioselectivity using

  （五甲基环戊二烯基）二氯化铑二聚体[RhCl 2 Cp *} 2 ]和由N- Boc保护的氨基酸和氨基醇形成的假二肽配体的组合，导致了高效且选择性的催化剂，用于2-酮的不对称转移加氢丙醇。使用这些原位形成的催化剂，以高收率和优异的对映选择性获得了许多不同的仲醇。氘标记实验表明，氢化物转移反应是通过单氢途径发生的。
• Synthesis and characterization of Co(<scp>ii</scp>) and Fe(<scp>ii</scp>) peptide conjugates as hydrolytic cleaving agents and their preferential enantiomeric disposition for CT-DNA: structural investigation of <scp>l</scp>-enantiomers by DFT and molecular docking studies
  作者：Sabiha Parveen、Mohammad Usman、Sartaj Tabassum、Farukh Arjmand

  DOI：10.1039/c5ra15742k

  日期：——

  Molecular docked model of Co(ii) peptide conjugate with DNA and the mechanism of hydrolytic cleavage of pBR322 DNA.

  Co（II）肽共轭物与DNA的分子对接模型及pBR322 DNA的水解裂解机制。
• Synthesis, characterization and in vitro DNA binding studies of tin(IV) complexes of tert-butyl 1-(2-hydroxy-1-phenylethylamino)-3-methyl-1-oxobutan-2-yl carbamate
  作者：Farukh Arjmand、Jamsheera A.

  DOI：10.1016/j.jorganchem.2011.08.009

  日期：2011.11

  Tin(IV) complexes 1(a and b) and 2(a and b) of valine derived peptide derivatives were synthesized and characterized on the basis of elemental analysis, IR, (1) H, C-13, Sn-119 NMR, ESI-MS spectra and molar conductance measurements. The C-Sn-C angle was estimated from C-I3 and H-1 NMR data (1)J(Sn-119, C-I3) = 623 Hz; solution (2)J(Sn-119, H-1) = 93.04 Hz to be 149.9 degrees. In vitro binding studies of complexes 1 and 2 under physiological conditions at room temperature with CT-DNA were carried out employing UV-visible, fluorescence, circular dichroism and viscometric studies. The binding affinity of the complexes was quantified by calculating the K-b values and it follows the order 2a > 1a > 2b > 1b. To further examine the specific mode of binding, the interaction of complexes 2(a and b) were carried out with 5'GMP and 5'TMP by using absorption and NMR (H-1, P-31) spectroscopy. The supercoiled pBR322 plasmid DNA cleavage activity of the complexes was ascertained by gel electrophoresis assay. The complexes cleave supercoiled pBR322 plasmid DNA efficiently into its nicked form at micromolar concentrations. (C) 2011 Elsevier B. V. All rights reserved.
• Employing the Structural Diversity of Nature: Development of Modular Dipeptide-Analogue Ligands for Ruthenium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones
  作者：Isidro M. Pastor、Patrik Västilä、Hans Adolfsson

  DOI：10.1002/chem.200304900

  日期：2003.9.5

  stereocenters, it was demonstrated that the absolute configuration of the product alcohol was determined by the configuration of the amino acid part of the ligand. Employing ligands based on L-amino acids generated S-configured products, and catalysts based on D-amino acids favored the formation of the R-configured alcohol. The combination N-Boc-L-alanine and (R)-phenylglycinol (Boc-L-Ab) or its enantiomer

  基于叔丁氧羰基（N-Boc）-保护的α-氨基酸和手性邻位氨基醇的组合，制备了新颖的二肽-类似物配体的文库。这些高度模块化的配体与[[RuCl（2）（p-cymene）]（2）]结合，并筛选得到的金属配合物作为催化剂，用于在转移氢化条件下使用2-丙醇作为氢供体的对苯乙酮对映选择性还原。用几种新颖的催化剂可获得极好的1-苯基乙醇对映体选择性（ee高达98％）。尽管大多数配体包含两个立体中心，但已证明产物醇的绝对构型是由配体的氨基酸部分的构型决定的。利用基于L-氨基酸的配体生成S-构型产物，基于D-氨基酸的催化剂有利于R-构型醇的形成。N-Boc-L-丙氨酸和（R）-苯基甘醇（Boc-L-Ab）或其对映异构体（N-Boc-D-丙氨酸和（S）-苯基甘醇，Boc-D-Aa）的组合被证明是还原过程的最佳配体。评估了许多芳基烷基酮的转移氢化反应，并获得了极佳的对映选择性，最高可达96％ee。
• Asymmetric transfer hydrogenation using amino acid derivatives; further studies and a mechanistic proposal
  作者：Aveline S.Y. Yim、Martin Wills

  DOI：10.1016/j.tet.2005.06.004

  日期：2005.8

  A series of investigations into the use of amino acid derivatives for the asymmetric catalysis of the transfer hydrogenation of ketones are presented. Based on the results observed, a mechanistic suggestion for the origin of the ellantioselective induction is proposed. (c) 2005 Elsevier Ltd. All rights reserved.