4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid methyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid methyl ester
• 英文别名: methyl 2-(4-methoxyphenyl)-4-methyl-5-oxo-4,5-dihydrooxazole-4-carboxylate；Methyl 2-(4-methoxyphenyl)-4-methyl-5-oxo-1,3-oxazole-4-carboxylate
• 化学式: C₁₃H₁₃NO₅
• 分子量: 263.25
• InChiKey: REJGQTTVWZQBLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  74.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-(4-methoxyphenyl)-4-methyloxazol-5-yl methyl 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84%的产率得到4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid methyl ester
  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

文献信息

• Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction
  作者：Takeshi Yamamoto、Ryo Murakami、Michinori Suginome

  DOI：10.1021/jacs.6b12349

  日期：2017.2.22

  Helically chiral poly(quinoxaline-2,3-diyl)s bearing 4-aminopyrid-3-yl pendants were synthesized as new helical-polymer-based chiral nucleophilic organocatalysts. The obtained chiral nucleophilic polymer catalysts exhibited high catalytic activity, enantioselectivity, and reusability in asymmetric Steglich rearrangement of oxazolyl carbonate to C-carboxyazlactone. The polyquinoxaline-based, helically

  带有 4-aminopyrid-3-yl 侧链的螺旋手性聚 (quinoxaline-2,3-diyl)s 被合成为新的基于螺旋聚合物的手性亲核有机催化剂。获得的手性亲核聚合物催化剂在恶唑基碳酸酯不对称 Steglich 重排为 C-羧基唑内酯中表现出高催化活性、对映选择性和可重复使用性。与已知的基于小分子的手性有机催化剂相比，基于聚喹喔啉的螺旋手性 DMAP 催化剂选择性介导分子内酰基转移，后者也介导分子间酰基转移。
• Organic base effects in NHC promoted O- to C-carboxyl transfer; chemoselectivity profiles, mechanistic studies and domino catalysis
  作者：Craig D. Campbell、Christopher J. Collett、Jennifer E. Thomson、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1039/c1ob05160a

  日期：——

  The O- to C-carboxyl transfer of oxazolyl carbonates promoted by triazolinylidenes, generated in situ with NEt3, shows a markedly different rate and chemoselectivity profile to the same reaction promoted by triazolinylidenes generated using KHMDS. The mechanism of these pathways has been probed through extensive crossover studies to understand this process. The use of NEt3 as a base allows domino multi-step

  由NEt 3原位产生的由三唑啉亚基促进的碳酸恶唑基碳酸酯的O - C羧基转移与由KHMDS生成的三唑啉亚基促进的相同反应显示出明显不同的速率和化学选择性。通过广泛的交叉研究探索了这些途径的机制，以了解这一过程。尽管手性NHC在这些多米诺反应过程中仅产生适度水平的不对称诱导（<15％ee），但使用NEt 3作为碱基可以开发出多米诺骨牌多步反应序列。
• Efficient N-Heterocyclic Carbene-Catalyzed <i>O</i>- to C-Acyl Transfer
  作者：Jennifer E. Thomson、Kathryn Rix、Andrew D. Smith

  DOI：10.1021/ol061380h

  日期：2006.8.1

  An N-heterocyclic carbene promotes the rearrangement of alpha-amino acid derived O-acyl carbonates to their corresponding C-acylated isomers, generating a C-C bond and a quaternary stereocenter with high efficiency, under mild reaction conditions and with low catalyst loadings.
• 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.