(1S,2R)-2-Ethoxy-1-((E)-styryl)-cyclopropanecarboxylic acid methyl ester

• 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: (1S,2R)-2-Ethoxy-1-((E)-styryl)-cyclopropanecarboxylic acid methyl ester
• 英文别名: methyl (1S,2R)-2-ethoxy-1-[(E)-2-phenylethenyl]cyclopropane-1-carboxylate
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: QFMIEQKRKVDGPE-YQPYWJPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R)-2-Ethoxy-1-((E)-styryl)-cyclopropanecarboxylic acid methyl ester 在 氯化二乙基铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 以68%的产率得到Methyl (3β,4α)-4-ethoxy-3-phenylcyclopent-1-ene-1-carboxylate
  参考文献：
  名称：

  Highly stereoselective [3 + 2] annulations by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids followed by a formally forbidden 1,3-sigmatropic rearrangement

  摘要：

  A highly stereoselective 3 + 2 annulation has been developed by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids to generate vinylcyclopropanes followed by a Et2AlCl-catalyzed 1,3-sigmatropic rearrangement. The success of this methodology rests on the remarkably stereoselectivity that is exhibited in both the cyclopropanation step and also the Et2AlCl-catalyzed vinylcyclopropane rearrangement.

  DOI：

  10.1021/jo00037a041
• 作为产物：
  描述：

  (E)-methyl 2-diazo-4-phenylbut-3-enoate 、 乙烯基乙醚 在 Rh₂(S-biTISP)2 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以53%的产率得到(1S,2R)-2-Ethoxy-1-((E)-styryl)-cyclopropanecarboxylic acid methyl ester
  参考文献：
  名称：

  Novel dirhodium tetraprolinate catalysts containing bridging prolinate ligands for asymmetric carbenoid reactions

  摘要：

  The D-2-symmetric dirhodium prolinate complex 3 is an effective catalyst for asymmetric vinylcarbenoid and phenylcarbenoid cyclopropanations. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01000-x

文献信息

• Asymmetric Cyclopropanations by Rhodium(II) <i>N</i>-(Arylsulfonyl)prolinate Catalyzed Decomposition of Vinyldiazomethanes in the Presence of Alkenes. Practical Enantioselective Synthesis of the Four Stereoisomers of 2-Phenylcyclopropan-1-amino Acid
  作者：Huw M. L. Davies、Paul R. Bruzinski、Debra H. Lake、Norman Kong、Michael J. Fall

  DOI：10.1021/ja9604931

  日期：1996.1.1

  to]dirhodium. The carbenoid structure has a critical effect on the degree of asymmetric induction, and the combination of a small electron-withdrawing group such as a methyl ester and an electron-donating group such as vinyl or phenyl resulted in the highest levels of enantioselectivity. The use of electron neutral alkenes and pentane as solvent also enhanced the enantioselectivity of the process.

  N-(芳基磺酰基)脯氨酸铑在烯烃存在下催化乙烯基重氮甲烷的分解导致以高度非对映选择性和对映选择性模式合成官能化环丙烷的非常通用的方法。进行了详细研究以确定控制该过程的对映选择性的关键因素。使用环状 N-(芳基磺酰基)氨基酸作为二铑催化剂的配体获得了最高水平的对映选择性，优化的催化剂是四[N-[(4-十二烷基苯基)磺酰基]-(L)-脯氨酰]二铑。卡宾结构对不对称诱导的程度有关键影响，小的吸电子基团（例如甲酯）和给电子基团（例如乙烯基或苯基）的组合导致最高水平的对映选择性。使用电子中性烯烃和戊烷作为溶剂也提高了该过程的对映选择性。这种化学的合成效用...
• Enantioselective synthesis of vinylcyclopropanes by rhodium(II) catalyzed decomposition of vinyldiazomethanes in the presence of alkenes
  作者：Huw M.L. Davies、Debra K. Hutcheson

  DOI：10.1016/s0040-4039(00)79298-7

  日期：1993.11

  Rhodium(II) N-(arenesulfonyl)prolinate catalyzed decomposition of vinyldiazomethanes in the presence of alkenes resulted in highly diastereoselective and enantioselective cyclopropanations.

  N-（芳烃磺酰基）脯氨酸铑（II）在烯烃存在下催化乙烯基重氮甲烷的分解导致高度非对映选择性和对映选择性环丙烷化。
• Asymmetric Synthesis of Cyclopentenes by [3 + 2] Annulations between Vinylcarbenoids and Vinyl Ethers
  作者：Huw M. L. Davies、Norman Kong、Melvyn Rowen Churchill

  DOI：10.1021/jo980738n

  日期：1998.9.1

  Rhodium N-(dodecylbenzenesulfonyl)prolinate [(Rh-2(S-DOSP)(4) (1)]-catalyzed decomposition of diazobutenoates in the presence of vinyl ethers results in highly diastereoselective and enantioselective synthesis of donor/acceptor-substituted vinylcyclopropanes. Diethylaluminum chloride-induced rearrangement of these vinylcyclopropanes results in the formation of cyclopentenes with excellent control of diastereoselectivity and for the fused cyclopentenes good control of absolute stereochemistry. This study illustrates the synthetic utility of Rh-2(S-DOSP)(4) as a chiral catalyst for vinylcarbenoid cyclopropanations and the remarkable diastereocontrol that is possible in the diethylaluminum chloride-induced ring expansion of donor/acceptor-substituted vinylcyclopropanes.
• Highly stereoselective [3 + 2] annulations by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids followed by a formally forbidden 1,3-sigmatropic rearrangement
  作者：Huw M. L. Davies、Baihua Hu

  DOI：10.1021/jo00037a041

  日期：1992.5

  A highly stereoselective 3 + 2 annulation has been developed by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids to generate vinylcyclopropanes followed by a Et2AlCl-catalyzed 1,3-sigmatropic rearrangement. The success of this methodology rests on the remarkably stereoselectivity that is exhibited in both the cyclopropanation step and also the Et2AlCl-catalyzed vinylcyclopropane rearrangement.
• Novel dirhodium tetraprolinate catalysts containing bridging prolinate ligands for asymmetric carbenoid reactions
  作者：Huw M.L. Davies、Stephen A. Panaro

  DOI：10.1016/s0040-4039(99)01000-x

  日期：1999.7

  The D-2-symmetric dirhodium prolinate complex 3 is an effective catalyst for asymmetric vinylcarbenoid and phenylcarbenoid cyclopropanations. (C) 1999 Elsevier Science Ltd. All rights reserved.