2-Cyclohex-2-enyl-2-(3-methyl-penta-1,2-dienyl)-malonic acid dimethyl ester | 552839-01-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-Cyclohex-2-enyl-2-(3-methyl-penta-1,2-dienyl)-malonic acid dimethyl ester
• CAS: 552839-01-7
• 化学式: C₁₇H₂₄O₄
• 分子量: 292.375
• InChiKey: HGMGZFIDOMJVMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  2-Cyclohex-2-enyl-2-(3-methyl-penta-1,2-dienyl)-malonic acid dimethyl ester 在 gold(III) chloride 、 silver hexafluoroantimonate 、 溶剂黄146 作用下， 以74%的产率得到methyl 3-(cyclohex-2-enyl)-6-ethyl-3,6-dihydro-6-methyl-2-oxo-2H-pyran-3-carboxylate
  参考文献：
  名称：

  Gold-Catalyzed Cyclization of Allene-Substituted Malonate Esters:  Synthesis of β,γ-Unsaturated δ-Lactones

  摘要：

  An efficient method for the preparation of beta,gamma-unsaturated delta-lactones has been developed. The starting materials for the synthesis of these compounds are allene-substituted malonates which undergo gold-catalyzed cyclization by means of nucleophilic attack of the ester moiety on the allene. It is worth mentioning that this is the first example where an ester group attacks as a nucleophile in a gold-catalyzed transformation of allenes.

  DOI：

  10.1021/ol070793v
• 作为产物：
  描述：

  3-乙酰氧基环己烯 在 palladium diacetate sodium hydride 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成 2-Cyclohex-2-enyl-2-(3-methyl-penta-1,2-dienyl)-malonic acid dimethyl ester
  参考文献：
  名称：

  PdII催化的烯丙基取代的烯烃的好氧烯丙基氧化碳环化：氧活化催化剂的固定化。

  摘要：

  DOI：

  10.1002/anie.200602421

文献信息

• An Unexpectedly Mild Thermal Alder−Ene-Type Cyclization of Enallenes
  作者：Katja Närhi、Johan Franzén、Jan-E. Bäckvall

  DOI：10.1021/jo060013g

  日期：2006.3.31

  A mild, thermal Alder−ene reaction of enallenes has been developed. The allenic double bond acts as the “ene” and generates a carbon−carbon bond to an unactivated olefinic “enophile” in DMF at 120 °C to give [n.3.0] bicyclic systems (n = 3−5) in good yields. Except for a minor [2 + 2] cycloaddition byproduct, the reaction proceeded with complete atom economy, as there is no requirement of a catalyst

  已经开发了温和的烯属烃热的Alder-ene反应。烯丙基双键充当“烯”，并在120°C下与未活化的烯烃“亲烯体”产生碳-碳键，从而以高收率得到[ n .3.0]双环体系（n = 3-5）。除了少量的[2 + 2]环加成副产物外，该反应以完全的原子经济性进行，因为不需要催化剂或其他反应物，并且在此过程中不会形成废产物。
• Carbon−Carbon Bond Formation in Palladium(II)-Catalyzed Allylic Oxidation:  A Novel Oxidative Carbocyclization of Allene-Substituted Olefins
  作者：Johan Franzén、Jan-E. Bäckvall

  DOI：10.1021/ja029505a

  日期：2003.5.1

  efficient palladium(II)-catalyzed oxidative carbocyclization has been developed. It was found that allene-substituted olefins 1 cyclized in the presence of 1 mol % Pd(O2CCF3)2 and p-benzoquinone (2 equiv) to give bicyclic ring systems 2 in good to excellent yields. The cyclization constitutes a new type of carbon-carbon bond forming reaction between an allene and an olefin under oxidative conditions

  开发了一种新的高效钯（II）催化氧化碳环化。发现丙二烯取代的烯烃1在1mol％Pd(O 2 CCF 3 ) 2 和对苯醌(2当量)存在下环化，以良好至极好的产率得到双环系统2。环化构成了丙二烯和烯烃在氧化条件下形成的新型碳-碳键形成反应。
• Palladium(0)-Catalyzed Cycloisomerization of Enallenes
  作者：Katja Närhi、Johan Franzén、Jan-E. Bäckvall

  DOI：10.1002/chem.200500303

  日期：2005.11.18

  A novel palladium(0)-catalyzed cycloisomerization of enallenes has been developed. This reaction, catalyzed by [Pd(dba)2] (dba=dibenzylideneacetone) in acetic acid, results in the formation of cyclopentene derivatives and [n.3.0]bicyclic systems (n=3, 4) in good to high yields. The carbon-carbon bond-forming step is highly stereoselective to give cis-fused bicyclic systems. The presence of acetic acid

  已开发了新型的钯（0）催化烯烯的环异构化。该反应由[Pd（dba）2]（dba =二亚苄基丙酮）在乙酸中催化，导致形成环戊烯衍生物和[n.3.0]双环体系（n = 3、4），产率高至高。碳-碳键形成步骤是高度立体选择性的，以产生顺式稠合双环系统。为了提供良好的反应性和区域选择性，反应中必不可少的是乙酸作为溶剂和dba作为钯（0）的配体存在。
• PdII-Catalyzed Aerobic Allylic Oxidative Carbocyclization of Allene-Substituted Olefins: Immobilization of an Oxygen-Activating Catalyst
  作者：Julio Piera、Katja Närhi、Jan-E. Bäckvall

  DOI：10.1002/anie.200602421

  日期：2006.10.20
• Gold-Catalyzed Cyclization of Allene-Substituted Malonate Esters:  Synthesis of <i>β</i>,<i>γ</i>-Unsaturated <i>δ</i>-Lactones
  作者：Julio Piera、Patrik Krumlinde、Dirk Strübing、Jan-E. Bäckvall

  DOI：10.1021/ol070793v

  日期：2007.5.1

  An efficient method for the preparation of beta,gamma-unsaturated delta-lactones has been developed. The starting materials for the synthesis of these compounds are allene-substituted malonates which undergo gold-catalyzed cyclization by means of nucleophilic attack of the ester moiety on the allene. It is worth mentioning that this is the first example where an ester group attacks as a nucleophile in a gold-catalyzed transformation of allenes.