2-(cyclohex-2-enyl)-2-methylmalonic acid dimethyl 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: 2-(cyclohex-2-enyl)-2-methylmalonic acid dimethyl ester
• 英文别名: dimethyl 2-(1,3-cyclohexanylallyl)-2-methylmalonate；dimethyl 2-[(1R)-cyclohex-2-en-1-yl]-2-methylpropanedioate
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: OCYIJPKJKPYSPX-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  甲基丙二酸二甲酯 、 1,3-环己二烯 在 allyl(cyclopentadiene)palladium(II) 、 1,3-双(二环己基磷)丙烷 作用下， 以 乙二醇二甲醚 为溶剂， 反应 24.0h， 以92%的产率得到2-(cyclohex-2-enyl)-2-methylmalonic acid dimethyl ester
  参考文献：
  名称：

  钯催化的单和二羰基化合物与共轭二烯的加成反应

  摘要：

  已经开发了分子间，钯催化的二羰基单羰基和1,3-二羰基化合物的α-CH键加成反应，并探索了与多种羰基化合物和腈反应的范围。CpPd（烯丙基）和可商购的1,3-双（二环己基膦基）丙烷（DCyPP）的组合以高收率催化了这些底物的CH键的1：1加成成二烯。这些反应包括不寻常地将酮，内酯，酯和腈的CH键加成至二烯，以及更常见的氰基酯，丙二腈和α-磺酰基酯的加成。报道了这些底物与环状和非环状二烯的反应。还进行了由非外消旋手性配体的配合物催化的反应，

  DOI：

  10.1021/jo0490999

文献信息

• Amino-P Ligands from Iminosugars: New Readily Available and Modular Ligands for Enantioselective Pd-Catalyzed Allylic Substitutions
  作者：Carlota Borràs、Pilar Elías-Rodríguez、Ana T. Carmona、Inmaculada Robina、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1021/acs.organomet.8b00140

  日期：2018.6.11

  requirements, using different C- and N-nucleophiles, with high enantioselectivities. Among the three groups of P,N-ligands (amino-P; P = phosphite, phosphinite, and phosphine groups) the new amino-phosphite ligands give the widest substrate and nucleophile scope, including the more challenging hindered linear and cyclic substrates. In particular, for carbohydrate-derived amino-phosphite ligands and linear substrates

  提出了一种新型的含有保护的吡咯烷-3，4-二醇部分的氨基亚磷酸酯/次膦酸酯/膦配体。这些配体是从容易获得的糖中获得的。因此，它们在选择立体异构性碳，能够调节电子和空间特性的多官能团以及碳水化合物衍生物的总体良好稳定性方面具有碳水化合物的优点。它们构成了一类新的P，N-配体，已用于具有不同对电子和空间要求的无环和环状底物的对映选择性烯丙基取代，使用不同的C-和N-亲核试剂，具有高对映选择性。在三组P，N-配体（氨基-P； P =亚磷酸酯，次亚膦酸酯，和膦基）新的氨基亚磷酸酯配体提供了最宽的底物和亲核试剂范围，包括更具挑战性的受阻线性和环状底物。特别是，对于碳水化合物衍生的氨基亚磷酸酯配体和线性底物，反应中的高对映选择性要求双萘基部分的R构型。然而，对于环状底物，通过列出亚磷酸二萘酯部分的手性可以得到两种产物对映体。还介绍了适当的Pd中间体的详细研究。
• Asymmetric Catalyzed Allylic Substitution Using a Pd/P–S Catalyst Library with Exceptional High Substrate and Nucleophile Versatility: DFT and Pd-π-allyl Key Intermediates Studies
  作者：Jèssica Margalef、Mercè Coll、Per-Ola Norrby、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1021/acs.organomet.6b00547

  日期：2016.10.10

  A large library of furanoside phosphite/phosphinite/phosphine-thioether ligands L1-L17a-1 has been applied in the Pd-catalyzed allylic substitution reactions of several substrate types using a wide range of nucleophiles. These ligands, which are prepared from inexpensive D-xylose, also incorporate the advantages of the heterodonor, the robustness of the thioether moiety, and the extra control provided by the flexibility of the chiral pocket through the presence of a biaryl phosphite group and a modular sugar backbone. By selecting the ligand components, we have been able to identify catalytic systems that can create new C-C, C-N, and C-O bonds in several substrate types (hindered and unhindered) using a wide range of nucleophiles in high yields and enantioselectivities (ee's up to >99%). Of particular note are the excellent enantioselectivities obtained in the etherification of linear and cyclic substrates, which represent the first example of successful etherification of both substrate types. The DFT computational study is in agreement with an early transition state. Further studies on the Pd-pi-allyl intermediates provided a deep understanding of the effect of ligand structure in the origin of enantioselectivity.
• Construction of P-stereogenic center by selective ligation of NPN type ligands and application to asymmetric allylic substitution reactions
  作者：Takamichi Yamagishi、Masatoshi Ohnuki、Takahiro Kiyooka、Dai Masui、Kiyoshi Sato、Motowo Yamaguchi

  DOI：10.1016/j.tetasy.2003.09.004

  日期：2003.10

  Chiral bisoxazolylphosphine ligands 1 [(S,S)-PhP(Ox-R)(2): R = Me, Pr-i, Bu-t] with an N-P-N backbone were prepared from chiral 4-alkyl-2-phenyl-4,5-dihydrooxazole compounds. These ligands coordinated to Pd(II) ion as bidentate ligands selectively to give a stereogenic phosphorus atom. The Pd-(S,S)-PhP(Ox-Bu-t)(2) 1c catalyst evoked high enantioselectivity in asymmetric allylic substitutions of acyclic substrates using dimethyl sodiomalonate as nucleophile. In the reaction of 3-penten-2-yl acetate, which affords a pi-allyl intermediate with a small steric factor, the Pd-1c catalyst successfully induced very high enantioselectivity (94% ee) indicating the effectiveness of the P-stereogenic center formed by selective ligation of ligand 1. In the reaction of cyclic substrates, moderate to high enantioselectivity was obtained by Pd-1 catalyst using the sodium salt of dimethyl methylmalonate. (C) 2003 Elsevier Ltd. All rights reserved.