(2R,3R)-(tert-butoxycarbonylamino)-3-(p-methoxyphenyl)-1,2-propanediol | 383420-35-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2R,3R)-(tert-butoxycarbonylamino)-3-(p-methoxyphenyl)-1,2-propanediol
• 英文别名: (2R,3R)-3-tert-butoxycarbonylamino-3-(4-methoxyphenyl)-1,2-propanediol；(1R,2R)-tert-butyl 2,3-dihydroxy-1-(p-methoxyphenyl)propylcarbamate；tert-butyl (1R,2R)-2,3-dihydroxy-1-(4-methoxyphenyl)propylcarbamate；(2R,3R)-3-tert-butoxycarbonyl-3-(4-methoxyphenyl)-1,2-propanediol；tert-butyl N-[(1R,2R)-2,3-dihydroxy-1-(4-methoxyphenyl)propyl]carbamate
• CAS: 383420-35-7
• 化学式: C₁₅H₂₃NO₅
• 分子量: 297.351
• InChiKey: QOWCUKPCDLJSLY-QWHCGFSZSA-N

物化性质

• 熔点：
  115-116 °C
• 沸点：
  484.6±45.0 °C(Predicted)
• 密度：
  1.171±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  88
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R)-(tert-butoxycarbonylamino)-3-(p-methoxyphenyl)-1,2-propanediol 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到(4R,5R)-cytoxazone
  参考文献：
  名称：

  的对映选择性合成（ - ） - cytoxazone和（+） -外延-cytoxazone通过铑催化的非对映选择性氧化C-H胺化

  摘要：

  有效的对映选择性合成（-）-cytoxazone（1）和（+）- epi- cytoxazone（2）的方法是脯氨酸催化醛的不对称α-氨基氧化，然后Rh催化非对映选择性氧化C–H胺化描述步骤。通过对氨基甲酸酯或氨基磺酸酯的C–H键进行Rh催化的分子内酰胺化，可获得具有良好或优异的非对映选择性的顺式或反式1,2-氨基醇。

  DOI：

  10.1016/j.tetlet.2006.11.016
• 作为产物：
  描述：

  methyl (2S,3R)-2-hydroxy-3-(4-methoxyphenyl)-3-[((R)-1-(4-methoxyphenyl)ethyl)amino]propionate 在 palladium dihydroxide sodium tetrahydroborate 、 偶氮二甲酸二异丙酯 、 氢气 、 碳酸氢钠 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 29.0h， 生成 (2R,3R)-(tert-butoxycarbonylamino)-3-(p-methoxyphenyl)-1,2-propanediol
  参考文献：
  名称：

  由β-内酰胺合成2-恶唑烷酮：（-）-cytoxazone及其所有立体异构体的立体有择全合成。

  摘要：

  首次描述了两种不同的抗生素构架（β-内酰胺类和2-恶唑烷酮）之间的合成相关性。在这种方法中，通过开环-环化异构化方法，由3-羟基β-内酰胺以立体异构纯的形式制备2-恶唑烷酮。证明了该方法在细胞因子调节剂（-）-cytoxazone及其三种立体异构体的总合成中的应用。[反应：请参见文字]。

  DOI：

  10.1021/ol062752p

文献信息

• Proline-Catalyzed α-Aminooxylation of β-Amino Aldehydes: Access to Enantiomerically Pure syn- and anti-3-Amino-3-aryl-1,2-alkanediols
  作者：Arumugam Sudalai、V. Venkataramasubramanian、I. Kiran

  DOI：10.1055/s-0034-1379735

  日期：——

  A new synthetic method for enantioselective synthesis of syn or anti -3-amino-3-aryl-1,2-alkanediols via proline catalyzed α-aminooxylation of β-amino aldehydes are described. This methodology is successfully applied to a concise and protecting group-free asymmetric synthesis of (–)-cytoxazone, (+)- epi -cytoxazone and formal synthesis of N-thiolated 2-oxazolidinone.

  描述了一种通过脯氨酸催化 β-氨基醛的 α-氨基氧化作用对映选择性合成顺式或反-3-氨基-3-芳基-1,2-烷二醇的新合成方法。该方法已成功应用于 (-)-胞恶酮、(+)- 表 - 胞恶唑的简洁且无保护基团的不对称合成和 N-硫醇化 2-恶唑烷酮的正式合成。
• Enantioselective synthesis of (−)-cytoxazone and (+)-epi-cytoxazone via Rh-catalyzed diastereoselective oxidative C–H aminations
  作者：Srinivasarao V. Narina、Talluri Siva Kumar、Shyla George、Arumugam Sudalai

  DOI：10.1016/j.tetlet.2006.11.016

  日期：2007.1

  An efficient enantioselective synthesis of (−)-cytoxazone (1) and (+)-epi-cytoxazone (2) using proline-catalyzed asymmetric α-amino-oxylation of aldehydes followed by Rh-catalyzed diastereoselective oxidative C–H amination as the key steps is described. syn or anti 1,2-aminoalcohols were obtained by Rh-catalyzed intramolecular amidation of the C–H bonds of carbamates or sulfamate esters with good to

  有效的对映选择性合成（-）-cytoxazone（1）和（+）- epi- cytoxazone（2）的方法是脯氨酸催化醛的不对称α-氨基氧化，然后Rh催化非对映选择性氧化C–H胺化描述步骤。通过对氨基甲酸酯或氨基磺酸酯的C–H键进行Rh催化的分子内酰胺化，可获得具有良好或优异的非对映选择性的顺式或反式1,2-氨基醇。
• Stereoselective synthesis of (−)-cytoxazone
  作者：A. Madhan、A.Ravi Kumar、B.Venkateswara Rao

  DOI：10.1016/s0957-4166(01)00340-8

  日期：2001.8

  A novel stereoselective synthesis of (−)-cytoxazone 1 was achieved via addition of p-methoxyphenylmagnesium bromide to the benzylimine derived from (S)-2,3-O-isopropylidene glyceraldehyde followed by one-step regioselective cyclization of N-Boc amino diol 7.

  通过向（S）-2,3- O-异亚丙基甘油醛衍生的苄基亚胺中添加对甲氧基苯基溴化镁，然后对N -Boc氨基二醇进行区域选择性环化，实现了（-）-cytoxazone 1的新型立体选择性合成7。
• NaIO4-mediated asymmetric bromohydroxylation of α,β-unsaturated carboxamides with high diastereoselectivity: a short route to (−)-cytoxazone and droxidopa
  作者：Shyla George、Srinivasarao V. Narina、Arumugam Sudalai

  DOI：10.1016/j.tetlet.2006.12.109

  日期：2007.2

  The NaIO4-mediated asymmetric bromohydroxylation of alpha,beta-unsaturated carboxamides was achieved using lithium bromide as the bromine source under acidic conditions at rt to afford the corresponding chiral alpha-bromo-beta-hydroxy carboxamides. Excellent yields (77-90%) and diastereoselectivities (up to 10:1) along with exclusive control over regio- as well as anti-selectivity are the main features with a good scope of substrates. The method has successfully been applied in the enantioselective syntheses of two biologically important molecules, viz (-)-cytoxazone and L-threo-DOPS (droxidopa). (c) 2007 Elsevier Ltd. All rights reserved.
• Dynamic Ligand Exchange of the Lanthanide Complex Leading to Structural and Functional Transformation:  One-Pot Sequential Catalytic Asymmetric Epoxidation-Regioselective Epoxide-Opening Process
  作者：Shin-ya Tosaki、Riichiro Tsuji、Takashi Ohshima、Masakatsu Shibasaki

  DOI：10.1021/ja043770+

  日期：2005.2.1

  The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various a,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samariurn azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.