(R)-4-((S)-1-hydroxy-1-methylprop-2-ynyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-4-((S)-1-hydroxy-1-methylprop-2-ynyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (4R)-4-[(2S)-2-hydroxybut-3-yn-2-yl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• 化学式: C₁₄H₂₃NO₄
• 分子量: 269.341
• InChiKey: FEDBCINNUNSKQP-YGRLFVJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  59
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-4-((S)-1-hydroxy-1-methylprop-2-ynyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester 在 盐酸 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 sodium chlorite 、 H₂O₄P^(1-)*Na⁽³⁺⁾ 、 碳酸氢钠 、 sodium carbonate 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 47.0h， 生成 benzyl 2-[[(2S,3R)-3-ethynyl-3-methyl-1-(2-nitrophenyl)sulfonylaziridine-2-carbonyl]amino]acetate
  参考文献：
  名称：

  Structure–activity relationships of ustiloxin analogues

  摘要：

  Four novel ustiloxin D analogues were synthesized focusing on the size of the macrocyclic core, the stereochemistry at the bridgehead ether, and the enantiomer of ustiloxin D. All four were subjected to biological evaluation testing the inhibition of tubulin polymerization. Only 2,2-dimethyl-ustiloxin D retained any activity. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.11.165
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 三氟化硼乙醚 、 碳酸氢钠 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 生成 (R)-4-((R)-1-hydroxy-1-methylprop-2-ynyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester 、 (R)-4-((S)-1-hydroxy-1-methylprop-2-ynyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Reactions of carbon nucleophiles with 2,2,3-trisubstituted ethynylaziridines

  摘要：

  Carbon nucleophiles were used to open a 2,2,3-trisubstituted ethynylaziridine. A cyanide nucleophile opened the ring at the more substituted carbon, proceeding regioselectively with inversion of configuration. In an attempt to expand upon the scope of the reaction, Normant cuprates were reacted with a 2,2,3-trisubstituted ethynylaziridine. This reaction produced chiral allenes via an anti-S(N)2' pathway. X-ray analysis of a derivative allowed the absolute stereochemistry of the anti-allenes to be assigned as P. Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2013.08.009

文献信息

• Total Synthesis of (+)-<i>ent</i>-Cyclizidine: Absolute Configurational Confirmation of Antibiotic M146791
  作者：Stephen Hanessian、Udaykumar Soma、Stéphane Dorich、Benoît Deschênes-Simard

  DOI：10.1021/ol103094j

  日期：2011.3.4

  The first total synthesis of the enantiomer of the indolizidine alkaloid, cyclizidine, was accomplished from readily available d-serine as the starting chiron. The relevant key reactions involve the stereocontrolled construction of the indolizidine ring system with the required functionality and further elaboration to install the cyclopropyl dienyl side chain. With this total synthesis, the absolute

  吲哚并立啶生物碱对映体环齐啶的第一个全合成是从容易获得的d-丝氨酸作为起始Chiron完成的。相关的关键反应涉及具有所需功能性的吲哚并咪唑环系统的立体控制结构，以及进一步详细的步骤以安装环丙基二烯基侧链。通过这种全合成，已经证实了基于重新确定其X射线结构的天然产物的绝对构型。
• A Regio- and Stereoselective Approach to Quaternary Centers from Chiral Trisubstituted Aziridines
  作者：Erin M. Forbeck、Cory D. Evans、John A. Gilleran、Pixu Li、Madeleine M. Joullié

  DOI：10.1021/ja0758077

  日期：2007.11.1

  formation of these hindered ethers has been investigated using a variety of functionalized aziridines and phenols to determine the scope of the reaction. Other nucleophiles, such as thiolate, azide, and chloride, have also been examined to encompass the synthesis of a broader range of functionalities. This aziridine ring opening reaction manifold has demonstrated utility in assembling: beta-substituted-alpha-amino

  对区域和立体特异性氮丙啶开环反应的彻底调查提出了用于构建各种季 β-取代-α-氨基官能团的新合成技术。温和、无金属的反应条件允许在高度功能化的系统中应用。该反应已应用于具有挑战性的叔烷基芳基醚的立体选择性形成。已经使用各种官能化氮丙啶和酚类研究了这些受阻醚的形成策略，以确定反应的范围。其他亲核试剂，如硫醇盐、叠氮化物和氯化物，也已被研究以涵盖更广泛的功能的合成。该氮丙啶开环反应歧管已证明可用于组装：β-取代-α-氨基甲酰胺、β-取代-α-氨基酯、β-取代-α-氨基甲硅烷基醚、β-硫代-α-氨基甲酰胺、β-叠氮基-α-氨基甲酰胺和β-卤代-α-氨基甲酰胺。探究氮丙啶取代模式影响的研究表明，烷基氮丙啶显示出与炔基氮丙啶相似的反应性，从而深入了解机理可能性。
• A Convergent Total Synthesis of Ustiloxin D via an Unprecedented Copper-Catalyzed Ethynyl Aziridine Ring-Opening by Phenol Derivatives
  作者：Pixu Li、Cory D. Evans、Madeleine M. Joullié

  DOI：10.1021/ol052287g

  日期：2005.11.1

  The ustiloxins are a family of heterodetic cyclopeptides that have been isolated from the water extracts of false smut balls on the panicles of rice plants caused by the fungus Ustilaginoidea virens. A concise total synthesis of ustiloxin D has been achieved via an unprecedented ethynyl aziridine ring-opening of phenol derivatives. The longest linear sequence of the synthesis is 15 steps from commercially available compounds.
• Reactions of carbon nucleophiles with 2,2,3-trisubstituted ethynylaziridines
  作者：Brandon T. Kelley、Madeleine M. Joullié

  DOI：10.1016/j.tetasy.2013.08.009

  日期：2013.10

  Carbon nucleophiles were used to open a 2,2,3-trisubstituted ethynylaziridine. A cyanide nucleophile opened the ring at the more substituted carbon, proceeding regioselectively with inversion of configuration. In an attempt to expand upon the scope of the reaction, Normant cuprates were reacted with a 2,2,3-trisubstituted ethynylaziridine. This reaction produced chiral allenes via an anti-S(N)2' pathway. X-ray analysis of a derivative allowed the absolute stereochemistry of the anti-allenes to be assigned as P. Published by Elsevier Ltd.
• Structure–activity relationships of ustiloxin analogues
  作者：Madeleine M. Joullié、Simon Berritt、Ernest Hamel

  DOI：10.1016/j.tetlet.2010.11.165

  日期：2011.4

  Four novel ustiloxin D analogues were synthesized focusing on the size of the macrocyclic core, the stereochemistry at the bridgehead ether, and the enantiomer of ustiloxin D. All four were subjected to biological evaluation testing the inhibition of tubulin polymerization. Only 2,2-dimethyl-ustiloxin D retained any activity. (C) 2011 Elsevier Ltd. All rights reserved.