benzyl (1-hydroxy-2-(hydroxymethyl)butan-2-yl)carbamate | 1346041-88-0

• 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: benzyl (1-hydroxy-2-(hydroxymethyl)butan-2-yl)carbamate
• 英文别名: (1,1-bis-(hydroxymethyl)propyl)carbamic acid benzyl ester；Carbamic acid, N-[1,1-bis(hydroxymethyl)propyl]-, phenylmethyl ester；benzyl N-[1-hydroxy-2-(hydroxymethyl)butan-2-yl]carbamate
• CAS: 1346041-88-0
• 化学式: C₁₃H₁₉NO₄
• 分子量: 253.298
• InChiKey: AWSRFAGFZCGQQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  464.0±45.0 °C(Predicted)
• 密度：
  1.193±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  78.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  焦磷酸四苄酯 、 benzyl (1-hydroxy-2-(hydroxymethyl)butan-2-yl)carbamate 在 titanium(IV) tetrabutoxide 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以96%的产率得到2-(benzyloxycarbonyl)amino-2-ethyl-3-hydroxylpropyl dibenzyl phosphate
  参考文献：
  名称：

  Selective phosphorylation of diols with a Lewis acid catalyst

  摘要：

  We report a method for the Lewis acid catalyzed phosphorylation of dials with pyrophosphates. Titanium alkoxides were found to be effective catalysts in the selective mono-phosphorylation for a range of dials. Dials of varying chain lengths and substituents were screened, to study the factors that influence mono-versus di-phosphorylation. It was discovered that 2-alkyl-2-amino-1,3-propanediols can be selectively mono-phosphoiylated in up to 97% isolated yield. This structural core is mono-phosphorylated in numerous immunomodulating compounds including the FDA-approved drug, FTY720.[GRAPHICS](C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.05.047
• 作为产物：
  描述：

  苯甲氧羰酰琥珀酰亚胺 、 2-氨基-2-乙基-1,3-丙二醇 以 四氢呋喃 为溶剂， 反应 16.0h， 以97%的产率得到benzyl (1-hydroxy-2-(hydroxymethyl)butan-2-yl)carbamate
  参考文献：
  名称：

  Carbonyl-Inserted Organo-Hybrids of a Dawson-Type Phosphovanadotungstate: Scope and Chemoselective Oxidation Catalysis

  摘要：

  The Dawson-type polyoxometalate (POM) [P2V3W15O62](9-) is a prototype for inclusion of carbonyls of amides, ureas, carbamates, and thiocarbamates into polyoxometallic structures. The carbonyl-inserted POMs catalyze the oxidation of sulfides. Chemoselectivity depends primarily on the proton content of the POM, but it Is also influenced by the organic substituent.

  DOI：

  10.1021/ol202430e

文献信息

• Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst
  作者：Erik T. Ouellette、Marshall G. Lougee、Andrea R. Bucknam、Paul J. Endres、John Y. Kim、Emma J. Lynch、Elizabeth J. Sisko、Bianca R. Sculimbrene

  DOI：10.1021/acs.joc.1c00414

  日期：2021.6.4

  incorporating a protected amine. The chiral ligand, base, solvent, and stoichiometry are evaluated along with a nonlinear effect study to support an active catalyst species that is oligomeric in chiral ligand. The use of pyrophosphates as the phosphorylating agent in the desymmetrization facilitates a user-friendly method for enantioselective phosphorylation with desirable protecting groups (benzyl, o-nitrobenzyl)

  讨论了通过磷酰基转移与钛-BINOLate 络合物对十个前手性二醇的去对称化。九个 1,3-丙二醇的磷酸化以 50-98% 的产率实现。对映体比率高达 92:8 的二醇可实现含有季 C-2 中心并结合受保护胺的二醇。手性配体、碱、溶剂和化学计量与非线性效应研究一起进行评估，以支持手性配体中的低聚活性催化剂种类。在去对称化中使用焦磷酸盐作为磷酸化剂促进了一种用户友好的方法，用于在磷酸盐产物上使用所需的保护基团（苄基，邻硝基苄基）进行对映选择性磷酸化。
• Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C–O Bond Coupling of Acyl Radicals
  作者：Zhang-Long Yu、Yong-Feng Cheng、Ji-Ren Liu、Wu Yang、Dan-Tong Xu、Yu Tian、Jun-Qian Bian、Zhong-Liang Li、Li-Wen Fan、Cheng Luan、Ang Gao、Qiang-Shuai Gu、Xin-Yuan Liu

  DOI：10.1021/jacs.3c00671

  日期：2023.3.22

  Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C–O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly

  迄今为止尚未实现过渡金属催化的酰基对映选择性功能化，这可能是由于它们相对较高的反应性，这使得化学和立体控制具有挑战性。在此，我们描述了 Cu(I) 催化的酰基自由基的对映选择性去对称 C-O 键偶联。该反应与（杂）芳基和烷基醛相容，更重要的是，它显示出非常广泛的具有挑战性的醇底物，例如 2,2-二取代的 1,3-二醇、2-取代的-2-氯-1、 3-二醇、2-取代的 1,2,3-三醇、2-取代的丝氨醇和内消旋伯 1,4-二醇，提供以具有挑战性的无环四取代碳立构中心为特征的富含对映体的酯。通过一步或两步的后续转型，该反应为从现成的醇（尤其是工业相关的甘油）快速制备手性 C3 结构单元提供了一种方便实用的策略。机理研究支持所提出的酰基自由基的 C-O 键偶联。
• Cu-catalysed enantioselective radical heteroatomic S–O cross-coupling
  作者：Yong-Feng Cheng、Zhang-Long Yu、Yu Tian、Ji-Ren Liu、Han-Tao Wen、Na-Chuan Jiang、Jun-Qian Bian、Guo-Xiong Xu、Dan-Tong Xu、Zhong-Liang Li、Qiang-Shuai Gu、Xin Hong、Xin-Yuan Liu

  DOI：10.1038/s41557-022-01102-z

  日期：2023.3

  The transition-metal-catalysed cross-coupling reaction has established itself as one of the most reliable and practical synthetic tools for the efficient construction of carbon–carbon/heteroatom (p-block elements other than carbon) bonds in both racemic and enantioselective manners. In contrast, development of the corresponding heteroatom–heteroatom cross-couplings has so far remained elusive, probably

  过渡金属催化的交叉偶联反应已成为高效构建碳-碳/杂原子的最可靠和实用的合成工具之一（p-除碳以外的嵌段元素）以外消旋和对映选择性方式键合。相比之下，迄今为止，相应的杂原子-杂原子交叉偶联的发展仍然难以捉摸，这可能是由于研究不足且通常具有挑战性的杂原子-杂原子还原消除。在这里，我们基于实验和理论结果展示了使用单电子还原消除作为在 Cu 催化下开发对映选择性 S-O 偶联的策略。该反应通过制备具有拥挤立体中心的具有挑战性的手性醇、生物质衍生的原料甘油的权宜之计以及肌醇的显着催化 4,6-去对称化，显示了其合成潜力。
• Selective phosphorylation of diols with a Lewis acid catalyst
  作者：Kyle A. Coppola、Joseph W. Testa、Emily E. Allen、Bianca R. Sculimbrene

  DOI：10.1016/j.tetlet.2014.05.047

  日期：2014.7

  We report a method for the Lewis acid catalyzed phosphorylation of dials with pyrophosphates. Titanium alkoxides were found to be effective catalysts in the selective mono-phosphorylation for a range of dials. Dials of varying chain lengths and substituents were screened, to study the factors that influence mono-versus di-phosphorylation. It was discovered that 2-alkyl-2-amino-1,3-propanediols can be selectively mono-phosphoiylated in up to 97% isolated yield. This structural core is mono-phosphorylated in numerous immunomodulating compounds including the FDA-approved drug, FTY720.[GRAPHICS](C) 2014 Elsevier Ltd. All rights reserved.
• Carbonyl-Inserted Organo-Hybrids of a Dawson-Type Phosphovanadotungstate: Scope and Chemoselective Oxidation Catalysis
  作者：Julie Oble、Benoît Riflade、Amandine Noël、Max Malacria、Serge Thorimbert、Bernold Hasenknopf、Emmanuel Lacôte

  DOI：10.1021/ol202430e

  日期：2011.11.18

  The Dawson-type polyoxometalate (POM) [P2V3W15O62](9-) is a prototype for inclusion of carbonyls of amides, ureas, carbamates, and thiocarbamates into polyoxometallic structures. The carbonyl-inserted POMs catalyze the oxidation of sulfides. Chemoselectivity depends primarily on the proton content of the POM, but it Is also influenced by the organic substituent.