(4R,2'R) 4-(2-hydroxy-2-butyl)-2,2-dimethyl-3-(tert-butoxycarbonyl)-oxazolidine | 167102-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4R,2'R) 4-(2-hydroxy-2-butyl)-2,2-dimethyl-3-(tert-butoxycarbonyl)-oxazolidine
• 英文别名: (R)-4-((R)-1-hydroxy-1-methylpropyl)-2,2-dimethyl oxazolidine-3-carboxylic acid tert-butyl ester；tert-butyl (4R)-4-[(2R)-2-hydroxybutan-2-yl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 167102-68-3
• 化学式: C₁₄H₂₇NO₄
• 分子量: 273.373
• InChiKey: MZKQDCVASWQJAA-QMTHXVAHSA-N

物化性质

• 熔点：
  75-76 °C
• 沸点：
  349.5±27.0 °C(Predicted)
• 密度：
  1.050±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  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：
  0.93
• 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：

  (4R,2'R) 4-(2-hydroxy-2-butyl)-2,2-dimethyl-3-(tert-butoxycarbonyl)-oxazolidine 在 盐酸 、 4-二甲氨基吡啶 、 偶氮二甲酸二异丙酯 、 水 、 sodium carbonate 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 生成 (2S,3S)-tert-butyldimethylsilyloxymethyl-2-ethyl-2-methyl-1-(2-nitrobenzenesulfonyl)aziridine
  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
• 作为产物：
  描述：

  tert-butyl N-[(1R)-1-(hydroxymethyl)-2-[methoxy(methyl)amino]-2-oxo-ethyl]carbamate 在 palladium on activated charcoal 、 三氟化硼乙醚 、 氢气 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 生成 (4R,2'R) 4-(2-hydroxy-2-butyl)-2,2-dimethyl-3-(tert-butoxycarbonyl)-oxazolidine
  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

• Evolution of the Total Syntheses of Ustiloxin Natural Products and Their Analogues
  作者：Pixu Li、Cory D. Evans、Yongzhong Wu、Bin Cao、Ernest Hamel、Madeleine M. Joullié

  DOI：10.1021/ja710363p

  日期：2008.2.1

  synthetically challenging chiral tertiary alkyl-aryl ether linkage. The first total synthesis of ustiloxin D was achieved in 31 linear steps using an S(N)Ar reaction. An NOE study of this synthetic product showed that ustiloxin D existed as a single atropisomer. Subsequently, highly concise and convergent syntheses of ustiloxins D and F were developed by utilizing a newly discovered ethynyl aziridine ring-opening

  Ustiloxins AF 是抗有丝分裂杂环肽，含有 13 元环状核心结构，具有合成上具有挑战性的手性叔烷基芳基醚键。使用 S(N)Ar 反应，通过 31 个线性步骤实现了 ustiloxin D 的首次全合成。该合成产品的 NOE 研究表明乌司洛辛 D 作为单一阻转异构体存在。随后，利用新发现的乙炔基氮丙啶开环反应，以 15 个步骤的最长线性序列开发了乌斯蒂洛辛 D 和 F 的高度简洁和收敛的合成方法。该方法进一步优化以实现更好的大环内酰胺化策略。通过第二代制备了乌斯蒂洛辛D、F和8个类似物（14-MeO-乌斯蒂洛辛D、4个C-6位氨基酸残基不同的类似物、以及3个(9R,10S)-表乌斯蒂洛辛类似物）路线。对这些化合物作为微管蛋白聚合抑制剂的评估表明，C-6 位的变化在一定程度上是可以容忍的。相反，C-9 甲氨基的 S 构型和游离酚羟基对于抑制微管蛋白聚合至关重要。
• 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。
• Total Synthesis of Ustiloxin D
  作者：Bin Cao、Haengsoon Park、Madeleine M. Joullié

  DOI：10.1021/ja017277z

  日期：2002.1.1

  The total synthesis of ustiloxin D, a highly potent inhibitor of microtubule assembly, has been achieved. Notable features are the use of nucleophilic aromatic substitution (SNAr) for the construction of a chiral tertiary alkyl-aryl ether linkage, Sharpless asymmetric aminohydroxylation for the formation of the beta-hydroxytyrosine moiety, macrolactamization, and regioselective methylation.
• Enantiospecific and diastereoselective synthesis of 4,4-disubstituted-3-amino-2-azetidinones, starting from D-serine
  作者：Giuseppina Ageno、Luca Banfi、Giuseppe Casciob Giuseppe Guanti、Elso Manghisi、Renata Riva、Valeria Rocca

  DOI：10.1016/0040-4020(95)00427-a

  日期：1995.7

  A strategy for the preparation of 4,4-disubstituted-3-amino-2-azetidinones which are useful intermediates for the synthesis of analogues of monosulfactam Tigemonam, was developed. It employs D-serine as chiral starting material and involves, as key steps, the diastereoselective addition of organometal compounds to ketones 9 and the stereospecific cyclization of tertiary alcohols 7 to the beta-lactams 6.
• 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.