1,1,1-trichloro-2-methylpropan-2-yl 2-(4-methoxyphenyl)-4-methyloxazol-5-yl carbonate | 880264-76-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1,1,1-trichloro-2-methylpropan-2-yl 2-(4-methoxyphenyl)-4-methyloxazol-5-yl carbonate
• 英文别名: 2-(4-methoxyphenyl)-4-methyloxazol-5-yl (1,1,1-trichloro-2-methylpropan-2-yl) carbonate；[2-(4-Methoxyphenyl)-4-methyl-1,3-oxazol-5-yl] (1,1,1-trichloro-2-methylpropan-2-yl) carbonate
• CAS: 880264-76-6
• 化学式: C₁₆H₁₆Cl₃NO₅
• 分子量: 408.666
• InChiKey: MHVFPVIUEGZUBZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  70.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,1,1-trichloro-2-methylpropan-2-yl 2-(4-methoxyphenyl)-4-methyloxazol-5-yl carbonate 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.08h， 以78%的产率得到1,1,1-trichloro-2-methylpropan-2-yl 2-(4-methoxyphenyl)-4-methyl-5-oxo-4,5-dihydrooxazole-4-carboxylate
  参考文献：
  名称：

  Probing the Efficiency of N-Heterocyclic Carbene Promoted O- to C-Carboxyl Transfer of Oxazolyl Carbonates

  摘要：

  Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.

  DOI：

  10.1021/jo702720a
• 作为产物：
  描述：

  2,2,2-三氯-1,1-二甲基乙基氯甲酸酯 、 2-(4-methoxyphenyl)-4-methyl-5-oxo-4,5-dihydrooxazole 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以65%的产率得到1,1,1-trichloro-2-methylpropan-2-yl 2-(4-methoxyphenyl)-4-methyloxazol-5-yl carbonate
  参考文献：
  名称：

  A Metallocene-Pyrrolidinopyridine Nucleophilic Catalyst for Asymmetric Synthesis

  摘要：

  A highly active chiral 4-aminopyridine nucleophilic catalyst, available in three steps from (S,S)-hexane-2,5-diol, was applied to the asymmetric Steglich rearrangement of O-aceylated azlactones (1 mol % loading, up to 76% ee).

  DOI：

  10.1021/ol053050n

文献信息

• Chiral Bicycle Imidazole Nucleophilic Catalysts: Rational Design, Facile Synthesis, and Successful Application in Asymmetric Steglich Rearrangement
  作者：Zhenfeng Zhang、Fang Xie、Jia Jia、Wanbin Zhang

  DOI：10.1021/ja109069k

  日期：2010.11.17

  A new type of chiral bicycle imidazole nucleophilic catalyst was rationally designed, facilely synthesized, and successfully applied in an asymmetric Steglich rearrangement with good to excellent yield and enantioselectivity at ambient temperature. Moreover, it can be easily recycled with almost no reduction of catalytic efficiency. This is the first example for the successful chiral imidazole nucleophilic

  一种新型手性双环咪唑亲核催化剂经过合理设计、简便合成，并成功应用于不对称 Steglich 重排，在室温下具有良好的产率和对映选择性。此外，它可以轻松回收，几乎不会降低催化效率。这是没有氢键辅助的手性咪唑亲核催化剂成功的第一个例子。
• Enantiodivergent Steglich rearrangement of O-carboxylazlactones catalyzed by a chirality switchable helicene containing a 4-aminopyridine unit
  作者：Chien-Tien Chen、Cheng-Che Tsai、Pei-Kang Tsou、Gou-Tao Huang、Chin-Hui Yu

  DOI：10.1039/c6sc02646j

  日期：——

  A pseudo-enantiomeric pair of optically switchable helicenes containing a catalytic 4-N-methylaminopyridine (MAP) bottom unit and a C2-symmetric, (10R,11R)-dimethoxymethyl-dibenzosuberane top template was synthesized. They underwent complementary photoswitching at 290 nm (P/M′, <1/>99) and 340 nm (P/M′, 91/9) and unidirectional thermo-rotation at 130 °C (P/M′, >99/<1). They were utilized to catalyze

  合成了含有催化的4- N-甲基氨基吡啶（MAP）底部单元和C 2对称（10 R，11 R）-二甲氧基甲基-二苯并亚戊烷顶部模板的可光学转换的螺旋对映体的对映体对映体。他们在290 nm（P / M '，<1 /> 99）和340 nm（P / M '，91/9）处进行互补光开关，并在130°C（P / M '，> 99 / <1）。它们被用来催化O-对C的对映异构Steglich重排。-羧基内酯，形成两种对映体，分别具有高达91％ee（R）和94％ee（S）的对映体。
• Chiral DMAP‐ <i>N</i> ‐oxides as Acyl Transfer Catalysts: Design, Synthesis, and Application in Asymmetric Steglich Rearrangement
  作者：Ming‐Sheng Xie、Ye‐Fei Zhang、Meng Shan、Xiao‐Xia Wu、Gui‐Rong Qu、Hai‐Ming Guo

  DOI：10.1002/anie.201812864

  日期：2019.2.25

  pyridine nitrogen, which serves as the nucleophilic site in the asymmetric acyl transfer reaction, we discovered that chiral DMAP‐N‐oxides, in which the oxygen now acts as the nucleophilic site, are efficient acyl transfer catalysts. Our finding might open a new door for the development of chiral DMAP‐N‐oxides for asymmetric acyl transfer reactions.

  开发，合成并以非对称Steglich重排为特征的DMAP‐ N-氧化物（以α-氨基酸为手性来源）。一系列O-酰化的内酯提供了高收率（高达97％的收率）和出色的对映体选择性（EE高达97％）的四级立体中心的C-酰化的内酯 。与在不对称酰基转移反应中用作亲核位点的吡啶氮的广泛使用相比，我们发现手性DMAP- N-氧化物（其中的氧气现在充当亲核位点）是有效的酰基转移催化剂。我们的发现可能为开发用于不对称酰基转移反应的手性DMAP‐ N-氧化物打开了新的大门。
• Probing the Efficiency of N-Heterocyclic Carbene Promoted <i>O</i>- to C-Carboxyl Transfer of Oxazolyl Carbonates
  作者：Jennifer E. Thomson、Craig D. Campbell、Carmen Concellón、Nicolas Duguet、Kathryn Rix、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/jo702720a

  日期：2008.4.1

  Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.
• A Metallocene-Pyrrolidinopyridine Nucleophilic Catalyst for Asymmetric Synthesis
  作者：Huy V. Nguyen、David C. D. Butler、Christopher J. Richards

  DOI：10.1021/ol053050n

  日期：2006.2.1

  A highly active chiral 4-aminopyridine nucleophilic catalyst, available in three steps from (S,S)-hexane-2,5-diol, was applied to the asymmetric Steglich rearrangement of O-aceylated azlactones (1 mol % loading, up to 76% ee).