(E)-cinnamyl 4-nitrophenyl carbonate | 959410-05-0

• 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: (E)-cinnamyl 4-nitrophenyl carbonate
• 英文别名: (4-nitrophenyl) [(E)-3-phenylprop-2-enyl] carbonate
• CAS: 959410-05-0
• 化学式: C₁₆H₁₃NO₅
• 分子量: 299.283
• InChiKey: UELDULXTGOBEGC-QPJJXVBHSA-N

物化性质

• 沸点：
  483.0±45.0 °C(predicted)
• 密度：
  1.297±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-cinnamyl 4-nitrophenyl carbonate 在 正丁基锂 、 二乙氨基乙醇 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 55.0h， 生成 (R)-3-phenyl-1-butene 、 (S)-3-phenyl-1-butene
  参考文献：
  名称：

  基于辅助SN2'反应的四元立体中心的不对称构建：1,7-相对立体形成的案例

  摘要：

  The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with phenylcopper or n-butylcopper to provide alkenes in moderate to good yields and with moderate to high enantioselectivities at the newly created quaternary stereogenic center. The E-carbamate with methyl and cyclohexyl substituents at the gamma-terminus provided the highest yield (87%) and enantioselectivity (>99.9:0.1 er) of all the substitution patterns tested. The corresponding Z-carbamate gave the lowest enantioselectivity observed (80.0:20.0). Carbamates with other substituents (n-butyl and t-butyl) at the E-terminal position gave moderate yields and enantioselectivities of alkenes. Cinnamyl substrates also provided good yields of alkenes with moderate enantioselectivities. The origin of enantioselectivity is analyzed in the context of dimeric lithioheterocuprate structures.

  DOI：

  10.3987/com-13-s(s)82
• 作为产物：
  描述：

  肉桂醇 、 对硝基苯基氯甲酸酯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以86%的产率得到(E)-cinnamyl 4-nitrophenyl carbonate
  参考文献：
  名称：

  Highly regioselective decarboxylative Claisen rearrangement reactions of diallyl 2-sulfonylmalonates

  摘要：

  The decarboxylative Claisen rearrangement of a range of substituted diallyl 2-sulfonylmalonates is described. The substrates are made by C-carboxylation of the corresponding allyl sulfonylacetates with allyl para-nitrophenyl carbonates. The reactions display a high degree of regioselectivity, with allylic substituents possessing electron-rich substituents at the allyl three-position rearranging preferentially. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.08.130

文献信息

• (Cyclopentadienyl)ruthenium-Catalyzed Regio- and Enantioselective Decarboxylative Allylic Etherification of Allyl Aryl and Alkyl Carbonates
  作者：Martina Austeri、David Linder、Jérôme Lacour

  DOI：10.1002/adsc.201000696

  日期：2010.12.17

  thenium hexafluorophosphate [CpRu(η6-naphthalene)][PF6]} in combination with a pyridine oxazoline ligand efficiently catalyze the decarboxylative allylic rearrangement of allyl aryl carbonates. Good levels of regio- and enantioselectivity are obtained. Starting from enantioenriched secondary carbonates, the reaction is stereospecific and the corresponding allylic ethers are obtained with net retention

  （环戊二烯基）三（乙腈）六氟磷酸钌[CPRU（NCMe）3 ] [PF 6 ]}或（环戊二烯基）（η 6 -萘）钌六氟磷酸盐[CPRU（η 6 -萘）] [PF 6]}与吡啶恶唑啉配体结合可有效催化碳酸烯丙酯的脱羧烯丙基重排。获得了良好的区域选择性和对映选择性。从对映体富集的仲碳酸酯开始，该反应是立体定向的，并且获得了具有净保留构型的相应的烯丙基醚。还使用碳酸烯丙烷基酯作为底物开发了这种转化的分子间形式。发现条件获得具有与分子内相似的选择性的相应产物过程。通过使用半不稳定的六配位磷酸抗衡离子，合成了两性离子的空气和水分稳定的手性钌络合物，并将其用于对映选择性醚化反应。这种高度亲脂性的金属络合物可以被回收并在随后的催化运行中有效地再利用。
• Regio- and Enantioselective Allylation of Phenols<i>via</i>Decarboxylative Allylic Etherification of Allyl Aryl Carbonates Catalyzed by (Cyclopentadienyl)ruthenium(II) Complexes and Pyridine-Hydrazone Ligands
  作者：Léo Egger、Cecilia Tortoreto、Thierry Achard、David Monge、Abel Ros、Rosario Fernández、José M. Lassaletta、Jérôme Lacour

  DOI：10.1002/adsc.201500534

  日期：2015.10.12

  (Cyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate [CpRu(CH3CN)3][PF6] in combination with pyridine-hydrazone ligands efficiently catalyzes the asymmetric decarboxylative allylic rearrangement of allyl aryl carbonates. Formation of CO bonds with high regio- and enantioselectivity ratios (up to 95:5 and 98% ee) is obtained. Good stereocontrol of the pseudotetrahedral geometry of the CpRu

  （环戊二烯基）三（乙腈）六氟磷酸钌[CpRu（CH 3 CN）3 ] [PF 6 ]与吡啶hydr配体结合可有效催化烯丙基芳基碳酸酯的不对称脱羧烯丙基重排。获得具有高区域和对映体选择性比率（高达95：5和98％ee）的CO键的形成。hydr配体可实现对CpRu部分伪四面体几何形状的良好立体控制，其六价配位的TRISPHAT-N阴离子的差向异构化证明了其“电子贫乏”的性质。
• Asymmetric Construction of Quaternary Stereogenic Centers via Auxiliary-Based SN2’ Reactions: A Case of 1,7-Relative Stereogenesis
  作者：Scott E. Denmark、Lyndon K. Marble

  DOI：10.3987/com-13-s(s)82

  日期：——

  The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with phenylcopper or n-butylcopper to provide alkenes in moderate to good yields and with moderate to high enantioselectivities at the newly created quaternary stereogenic center. The E-carbamate with methyl and cyclohexyl substituents at the gamma-terminus provided the highest yield (87%) and enantioselectivity (>99.9:0.1 er) of all the substitution patterns tested. The corresponding Z-carbamate gave the lowest enantioselectivity observed (80.0:20.0). Carbamates with other substituents (n-butyl and t-butyl) at the E-terminal position gave moderate yields and enantioselectivities of alkenes. Cinnamyl substrates also provided good yields of alkenes with moderate enantioselectivities. The origin of enantioselectivity is analyzed in the context of dimeric lithioheterocuprate structures.
• Highly regioselective decarboxylative Claisen rearrangement reactions of diallyl 2-sulfonylmalonates
  作者：Donald Craig、Mark I. Lansdell、Simon E. Lewis

  DOI：10.1016/j.tetlet.2007.08.130

  日期：2007.10

  The decarboxylative Claisen rearrangement of a range of substituted diallyl 2-sulfonylmalonates is described. The substrates are made by C-carboxylation of the corresponding allyl sulfonylacetates with allyl para-nitrophenyl carbonates. The reactions display a high degree of regioselectivity, with allylic substituents possessing electron-rich substituents at the allyl three-position rearranging preferentially. (C) 2007 Elsevier Ltd. All rights reserved.