1-[1-(4-chloro-phenyl)-2-nitro-ethyl]-2-oxo-cyclopentanecarboxylic acid methyl ester | 1167427-70-4

• 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: 1-[1-(4-chloro-phenyl)-2-nitro-ethyl]-2-oxo-cyclopentanecarboxylic acid methyl ester
• 英文别名: 1-[1-(4-chlorophenyl)-2-nitroethyl]-2-oxo-cyclopentanecarboxylic acid methyl ester；methyl 1-[1-(4-chlorophenyl)-2-nitroethyl]-2-oxocyclopentane-1-carboxylate
• CAS: 1167427-70-4
• 化学式: C₁₅H₁₆ClNO₅
• 分子量: 325.749
• InChiKey: KWBOWMXRKJHZKZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  86.51
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  1-(4-氯苯基)-2-硝基乙烯 、 2-氧代环戊羧酸乙酯 在 1-[2-[Bis[2-[(2,3,4,5,6-pentafluorophenyl)carbamoylamino]ethyl]amino]ethyl]-3-(2,3,4,5,6-pentafluorophenyl)urea 作用下， 以 二甲基亚砜 为溶剂， 反应 6.0h， 以94%的产率得到1-[1-(4-chloro-phenyl)-2-nitro-ethyl]-2-oxo-cyclopentanecarboxylic acid methyl ester
  参考文献：
  名称：

  Tris-ureas as versatile and highly efficient organocatalysts for Michael addition reactions of nitro-olefins: Mechanistic insight from in-situ diagnostics

  摘要：

  Tris(2-aminoethyl)-amine, TREN based tris-ureas (1a-1d) and tris-thiourea (1e) have been explored towards a wide range of catalytic Michael addition reactions. These tris-ureas, 1a-1d efficiently catalyze the addition reaction of beta-nitro styrenes (2a-2d) with various nucleophiles such as beta-ketoesters (3a-3c), 1,3-dicarbonyl compound (3d), a cyanoester (3e) and a nitroester (3f) under ambient conditions to produce corresponding nitro alkanes in high yields. Pentafluorophenyl attached tris-urea, 1d is found to be the most effective catalyst in the series that yields 78-98% products conversion. In case of the reaction between beta-nitro styrenes and malononitrile (3g) in presence of 1d, 2-amino-5-nitro-4,6-diphenylcyclohex-1-ene-1,3,3-tricarbonitriles are also isolated as a minor product along with the corresponding Michael adduct. The added advantage of bridge-head nitrogen center in tris-urea organocatalysts, 1a-1d has been established by studying analogous benzene platform based tris-ureas (1f, 1g, 1h) in similar experimental conditions. Furthermore, a plausible reaction mechanism has also been established based on in-situ H-1 NMR kinetic studies. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.01.004

文献信息

• Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Nitroalkenes Promoted by a Bifunctional Homobimetallic Co2-Schiff Base Complex
  作者：Makoto Furutachi、Zhihua Chen、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.3390/molecules15010532

  日期：——

  Catalytic asymmetric 1,4-addition of β-keto esters to nitroalkenes is described. 2.5 mol % of a homobimetallic Lewis acid/Brønsted base bifunctional Co2-Schiff base complex smoothly promoted the reaction in excellent yield (up to 99%), diastereoselectivity, and enantioselectivity (up to >30:1 dr and 98% ee). Catalyst loading was successfully reduced to 0.1 mol %. Mechanistic studies suggested that

  描述了 β-酮酯与硝基烯烃的催化不对称 1,4-加成反应。2.5 mol% 的均双金属路易斯酸/Brønsted 碱双功能 Co2-Schiff 碱配合物以优异的产率（高达 99%）、非对映选择性和对映选择性（高达 >30:1 dr 和 98% ee）顺利促进反应。催化剂负载成功地降低到 0.1 mol%。机理研究表明，两个 Co 金属中心的分子内协同功能对于高催化活性和立体选择性很重要。
• Sugar Based γ-Amino Alcohol Organocatalyst for Asymmetric Michael Addition of β-Keto Esters with Nitroolefins
  作者：Hiroto Nakano、Divakar Ganesan、Madhu Chennapuram、Zubeda Begum、Chigusa Seki、Yuko Okuyama、Eunsang Kwon、Koji Uwai、Michio Tokiwa、Suguru Tokiwa、Mitsuhiro Takeshita

  DOI：10.3987/com-19-14172

  日期：——

  Division of Sustainable and Environmental Engineering, Graduate School of Engineering, Muroran Institute of Technology, 27-1 Mizumoto-cho, Muroran 050-8585, E-mail: [e-mail] Tohoku Medical and Pharmaceutical University, 4-4-1 Komatsushima, Aoba-Ku, Sendai 981-8558, Japan, E-mail: [e-mail] Research and Analytical Center for Giant Molecules, Graduate School of Sciences

  室兰工业大学工学研究生院可持续与环境工学部，室兰水本町27-1 050-8585，电子邮件：[e-mail] 东北医科大学， 4-4-1 Komatsushima, Aoba-Ku, Sendai 981-8558, Japan, E-mail: [e-mail] 东北大学研究生院大分子研究和分析中心, 6-3 Aoba, Aramaki, Aoba-Ku, Sendai 980-8578, Japan, E-mail: [e-mail] Tokiwakai Group, 62 Numajiri Tsuduri-Chou Uchigo Iwaki 973-8053, Japan, E-mail: hisyo@tokiwa.或.jp
• Amino Amide Organocatalysts for Asymmetric Michael Addition of β-Keto Esters with β-Nitroolefins
  作者：Isiaka Alade Owolabi、Madhu Chennapuram、Chigusa Seki、Yuko Okuyama、Eunsang Kwon、Koji Uwai、Michio Tokiwa、Mitsuhiro Takeshita、Hiroto Nakano

  DOI：10.1246/bcsj.20180302

  日期：2019.3.15

  Asymmetric Michael addition of β-keto esters with trans-β-nitroolefins using chiral amino amide organocatalyst was tried and afforded synthetically useful chiral Michael adducts in both excellent c...

  使用手性氨基酰胺有机催化剂尝试了β-酮酯与反式-β-硝基烯烃的不对称迈克尔加成，并以两种优异的方式提供了合成有用的手性迈克尔加合物。
• 2-Azanorbornane-Based Amino Alcohol Organocatalysts for Asymmetric Michael Reaction of β-Keto Esters with Nitroolefins
  作者：Rei Togashi、Madhu Chennapuram、Chigusa Seki、Yuko Okuyama、Eunsang Kwon、Koji Uwai、Michio Tokiwa、Mitsuhiro Takeshita、Hiroto Nakano

  DOI：10.1002/ejoc.201900308

  日期：2019.6.30

  A highly enantioselective Michael addition of β‐keto esters to nitroolefins was carried out using newly designed optically active 2‐azanorbornane‐based amino alcohol organocatalysts to produce the corresponding chiral Michael adducts in good chemical yields (up to 99 %) and stereoselectivities (up to dr = 91:9, up to 91 % ee).

  使用新设计的光学活性的基于2-氮杂降冰片烷的氨基醇有机催化剂，对β-酮酯向硝基烯烃进行了高对映选择性的迈克尔加成反应，从而以良好的化学收率（高达99％）和立体选择性（高达dr = 91：9，最高可达91％ee）。
• A Stable Homodinuclear Biscobalt(III)-Schiff Base Complex for Catalytic Asymmetric 1,4-Addition Reactions of β-Keto Esters to Alkynones
  作者：Zhihua Chen、Makoto Furutachi、Yuko Kato、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1002/anie.200805967

  日期：2009.3.9

  Two metal cooperation: A homodinuclear Co2–Schiff base complex Co2(OAc)2–1 promoted the asymmetric 1,4‐addition of β‐keto esters to alkynones under solvent‐free conditions in air (see scheme). The reactions proceeded without air or moisture sensitivity in high yields and with high enantioselectivities (99–91 % ee) at room temperature under highly concentrated conditions (neat–20 M) with 0.1–2.5 mol %

  两个金属合作：一个同双核钴2 -Schiff碱配合物共2（OAC）2 - 1促进了不对称1,4-加成β酮酯的对alkynones无溶剂条件下，在空气中（参见方案）。反应在没有空气或湿气敏感性的情况下以高收率进行，在室温和高浓度条件下（纯净20 M），催化剂负载量为0.1到2.5 mol％时，具有高对映选择性（99-91％ee）  。