methyl (+/-)-4-methoxy-2-oxo-3-cyclohexene-1-carboxylate | 91817-43-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (+/-)-4-methoxy-2-oxo-3-cyclohexene-1-carboxylate
• 英文别名: methy-4-methoxy-2-oxo-3-cyclohexene carboxylate；methyl 4-methoxy-2-oxo-3-cyclohexenecarboxylate；methyl 4-methoxy-2-oxocyclohex-3-enecarboxylate；Methyl 4-methoxy-2-oxocyclohex-3-ene-1-carboxylate
• CAS: 91817-43-5
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: CSDNBWAVBNQZMH-UHFFFAOYSA-N

物化性质

• 沸点：
  298.8±40.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-cyclohexylprop-2-yn-1-yl acetate 、 methyl (+/-)-4-methoxy-2-oxo-3-cyclohexene-1-carboxylate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 potassium phosphate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 二甲基亚砜 为溶剂， 以78%的产率得到6-cyclohexyl-4-methoxy-7-methylene-2-oxobicyclo[3.2.1]oct-3-ene-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Diastereoselective Construction of 7-Methylenebicyclo[3.2.1]oct-3-en-2-one Derivatives by Palladium-Catalyzed Cyclization of Propargylic Acetates with 2-Oxocyclohex-3-enecarboxylates

  摘要：

  The reaction of propargylic acetates with 2-oxocyclohex-3-enecarboxylates in the presence of a palladium catalyst is described. Substituted 7-methylenebicyclo[3.2.1]oct-3-en-2-ones were synthesized in a highly diastereoselective manner.

  DOI：

  10.1021/ol201243u
• 作为产物：
  描述：

  1,3-环己二酮 在 sodium hydride 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 甲醇 、 苯 为溶剂， 反应 17.33h， 生成 methyl (+/-)-4-methoxy-2-oxo-3-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Organoiron complexes in organic synthesis. 33. Tricarbonylcyclohexadienyliron complexes as aryl cation equivalents: a formal synthesis of (.+-.)-O-methyljoubertiamine

  摘要：

  DOI：

  10.1021/jo00195a003

文献信息

• Divergent reactivity in tandem reduction-Michael ring closures of five- and six-membered cyclic enones
  作者：Richard A. Bunce、Baskar Nammalwar、LeGrande M. Slaughter

  DOI：10.1002/jhet.111

  日期：2009.9

  with the six-ring substrate reacting at the ester carbonyl and the five-ring substrate closing on the enone double bond. The difference in reactivity is attributed to the conformational flexibility, relative reactivity, and steric environment of C4-substituted six- and five-membered cyclic enones. J. Heterocyclic Chem., (2009).

  在这项研究中，（±）-1-（2-硝基苄基）-4-氧代-2-环己烯-1-羧酸甲酯和（±）-（2-硝基苄基）-4-氧代-2-环戊烯-1-甲酯制备羧酸盐并在溶解金属条件下进行还原环化。两种反应物表现出不同的行为，六环底物在酯羰基上反应，而五环底物在烯酮双键上闭合。反应性的差异归因于C4取代的六元和五元环状烯酮的构象柔韧性，相对反应性和空间环境。J.杂环化​​学，（2009）。
• Total Syntheses of (±)-Platencin and (−)-Platencin
  作者：K. C. Nicolaou、G. Scott Tria、David J. Edmonds、Moumita Kar

  DOI：10.1021/ja906801g

  日期：2009.11.4

  The secondary metabolites platensimycin and platencin, isolated from the bacterial strain Streptomyces platensis, represent a novel class of natural products exhibiting unique and potent antibacterial activity. Platencin, though structurally similar to platensimycin, has been found to operate through a slightly different mechanism of action involving the dual inhibition of lipid elongation enzymes

  从细菌菌株钝顶链霉菌中分离出的次生代谢物钝顶霉素和钝顶霉素代表了一类新型天然产物，具有独特而有效的抗菌活性。Platencin 虽然在结构上与 Platensimycin 相似，但已发现其作用机制略有不同，涉及脂质延伸酶 FabF 和 FabH 的双重抑制。这两种天然产物对主要抗生素耐药菌株（包括耐甲氧西林金黄色葡萄球菌、耐万古霉素金黄色葡萄球菌和耐万古霉素屎肠球菌）均表现出强效、广谱、革兰氏阳性抗菌活性。本文描述了我们对血小板素的合成努力，最终得到了天然产物的外消旋和不对称制备。该合成证明了钴催化的不对称狄尔斯-阿尔德反应和[3.2.1]双环酮一锅还原重排为[2.2.2]双环烯烃的能力。
• Asymmetric Allylic Alkylation of β-Ketoesters with Allylic Alcohols by a Nickel/Diphosphine Catalyst
  作者：Yusuke Kita、Rahul D. Kavthe、Hiroaki Oda、Kazushi Mashima

  DOI：10.1002/anie.201508757

  日期：2016.1.18

  Asymmetric allylic alkylation of β‐ketoesters with allylic alcohols catalyzed by [Ni(cod)2]/(S)‐H8‐BINAP was found to be a superior synthetic protocol for constructing quaternary chiral centers at the α‐position of β‐ketoesters. The reaction proceeded in high yield and with high enantioselectivity using various β‐ketoesters and allylic alcohols, without any additional activators. The versatility of

  发现[Ni（cod）2 ] /（S）-H 8 -BINAP催化的烯丙基醇与β-酮酯的不对称烯丙基烷基化是在β-酮酯的α-位上构建季手性中心的优良合成方案。使用各种β-酮酸酯和烯丙基醇，无需任何其他活化剂，即可以高收率和高对映选择性进行反应。展示了这种方法在获取有用和对映体富集产品方面的多功能性。
• Palladium-catalyzed cross-coupling reactions of arylmetal compounds with β-substituted α-iodoenones and a cyclohexyl triflate
  作者：Folkert Boße、Ashok Rao Tunoori、AndréJ. Niestroj、Oliver Gronwald、Martin E. Maier

  DOI：10.1016/0040-4020(96)00489-9

  日期：1996.7

  Electron-rich arylstannanes were found to couple with α-iodoenones in the presence of Pd2(dba)3·CHCl3, a weak-coordinating ligand [AsPh3 or Pd(o-tol)3] and CuI (0.75-1.0 equiv) to give sterically hindered α-arylcyclohexenones 15–20. In addition, compounds 19, 22 and 23 were prepared by Suzuki coupling reactions of the cyclohexyl derivatives 7c,f and 11, respectively, with the arylboronic acid 21.

  发现在存在弱配位配体[AsPh 3或Pd（邻甲苯基）3 ]和CuI（0.75-1.0当量）的Pd 2（dba）3 ·CHCl 3的存在下，富电子芳基斯坦酮与α-碘代烯偶联。）可得到空间受阻的α-芳基环己烯酮15–20。另外，分别通过环己基衍生物7c，f和11与芳基硼酸21的Suzuki偶联反应制备化合物19、22和23。
• Diastereoselective Construction of 7-Methylenebicyclo[3.2.1]oct-3-en-2-one Derivatives by Palladium-Catalyzed Cyclization of Propargylic Acetates with 2-Oxocyclohex-3-enecarboxylates
  作者：Masahiro Yoshida、Chiyuki Sugimura、Kozo Shishido

  DOI：10.1021/ol201243u

  日期：2011.7.1

  The reaction of propargylic acetates with 2-oxocyclohex-3-enecarboxylates in the presence of a palladium catalyst is described. Substituted 7-methylenebicyclo[3.2.1]oct-3-en-2-ones were synthesized in a highly diastereoselective manner.