dimethyl 2-hexenylmalonate | 74810-84-7

• 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: dimethyl 2-hexenylmalonate
• 英文别名: Dimethyl 2-hex-2-enylpropanedioate
• CAS: 74810-84-7
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: OFOCVWIEUIHRMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  dimethyl 2-hexenylmalonate 在 sodium hydride 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 32.0h， 生成
  参考文献：
  名称：

  Water Control over the Chemoselectivity of a Ti/Ni Multimetallic System: Heck- or Reductive-Type Cyclization Reactions of Alkyl Iodides

  摘要：

  A versatile Ti/Ni multimetallic protocol is described for the efficient catalysis of two different reactions, namely a Heck- and reductive-type cyclization of alkyl iodides, in the absence or presence of water, respectively. Noteworthy, the versatility of Ti(III) chemistry allows an oxidative ending step under reductive conditions to give Heck-type products, and the good H-atom transfer capabilities of Ti(III)-aqua complexes ensure reductive-type cyclizations.

  DOI：

  10.1021/ol3028913
• 作为产物：
  描述：

  1-bromo-2-hexene 、 丙二酸二甲酯 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 16.0h， 以47%的产率得到dimethyl 2-hexenylmalonate
  参考文献：
  名称：

  Water Control over the Chemoselectivity of a Ti/Ni Multimetallic System: Heck- or Reductive-Type Cyclization Reactions of Alkyl Iodides

  摘要：

  A versatile Ti/Ni multimetallic protocol is described for the efficient catalysis of two different reactions, namely a Heck- and reductive-type cyclization of alkyl iodides, in the absence or presence of water, respectively. Noteworthy, the versatility of Ti(III) chemistry allows an oxidative ending step under reductive conditions to give Heck-type products, and the good H-atom transfer capabilities of Ti(III)-aqua complexes ensure reductive-type cyclizations.

  DOI：

  10.1021/ol3028913

文献信息

• Features and Applications of [Rh(CO)₂Cl]₂-Catalyzed Alkylations of Unsymmetrical Allylic Substrates
  作者：Brandon L. Ashfeld、Kenneth A. Miller、Anna J. Smith、Kristy Tran、Stephen F. Martin

  DOI：10.1021/jo701290b

  日期：2007.11.1

  A novel regio- and stereoselective [Rh(CO)2Cl]2-catalyzed allylic alkylation of unsymmetrical allylic carbonates was discovered. The regioselectivity of the reaction favors product ratios in which substitution occurs at the carbon bearing the leaving group. When an enantiomerically enriched carbonate (≥99% ee) was examined, the Rh(I)-catalyzed allylic alkylation proceeded stereoselectively to provide

  发现了一种新的区域和立体选择性[Rh（CO）2 Cl] 2催化的不对称烯丙基碳酸酯的烯丙基烷基化反应。反应的区域选择性有利于产物比率，其中取代发生在带有离去基团的碳上。当检查对映体富集的碳酸盐（≥99％ee）时，Rh（I）催化的烯丙基烷基化立体选择性地进行，以提供保留绝对立体化学（98％ee）的烷基化产物。确定[Rh（CO）2 Cl] 2的范围-催化的烯丙基烷基化，检查了各种碳原子和杂原子亲核试剂，并描述了结果。作为Rh（I）催化的烯丙基烷基化的一种应用，已开发了一系列新颖的多米诺骨牌反应，这些反应将独特的区域和立体选择性[Rh（CO）2 Cl] 2催化的烯丙基三氟乙酸烷基化与分子内鲍森偶联-Khand环化，环异构化或[5 + 2]环加成。所描述方法的一个独特方面是使用单个催化剂进行顺序转化，其中只需控制反应温度即可调节催化活性。这种方法的实施提供了从简单的前体快速有效地进入各种双环碳骨架的途径。
• Ruthenium Complexes Bearing Bulky Pentasubstituted Cyclopentadienyl Ligands and Evaluation of [Ru(η ⁵ ‐C ₅ Me ₄ R)(MeCN) ₃ ][PF ₆ ] Precatalysts in Nucleophilic Allylic Substitution Reactions
  作者：Hui‐Jun Zhang、Bernard Demerseman、Zhenfeng Xi、Christian Bruneau

  DOI：10.1002/ejic.200800295

  日期：2008.7

  [Ru(η5-C5Me4R)(MeCN)3][PF6] (R = CH2tBu, iPr, tBu, and CF3; 2–5) complexes were synthesized in two steps starting from the appropriate cyclopentadienes and RuCl3·3H2O. The fully substituted ruthenocenes [Ru(C5Me5)(C5Me4R*)], [Ru(C5Me5)(C5nPr4R*)] R* = (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl} and [Ru(C5Me5)(C5nPr5)] were obtained by treating [Ru(C5Me5)Cl]4 with the corresponding cyclopentadienyllithium

  [Ru(η5-C5Me4R)(MeCN)3][PF6] (R = CH2tBu, iPr, tBu, 和 CF3; 2-5) 配合物从适当的环戊二烯和 RuCl3·3H2O 开始，分两步合成。完全取代的钌茂 [Ru(C5Me5)(C5Me4R*)], [Ru(C5Me5)(C5nPr4R*)] R* = (1R,5S)-6,6-二甲基双环[3.1.1]hept-2-en -2-yl} 和 [Ru(C5Me5)(C5nPr5)] 是通过用相应的环戊二烯基锂盐处理 [Ru(C5Me5)Cl]4 获得的。将配合物 2-5 评估为亲核烯丙基取代反应的催化剂前体，并将结果与​​使用 [Ru(C5Me5)(MeCN)3][PF6] (1) 预催化剂获得的结果进行比较。
• Allyl 4-Chlorophenyl Sulfone as a Versatile 1,1-Synthon for Sequential α-Alkylation/Cobalt-Catalyzed Allylic Substitution
  作者：Masahiro Kojima、Shigeki Matsunaga、Tomoyuki Sekino、Shunta Sato、Kazuki Kuwabara、Koji Takizawa、Tatsuhiko Yoshino

  DOI：10.1055/s-0040-1707524

  日期：2020.7

  rare 1,1-dipole synthons, allyl sulfones are rarely used in target-oriented syntheses, likely due to the lack of a general catalytic method for their branch-selective allylic substitution. Herein, we identified allyl 4-chlorophenyl sulfone as a versatile linchpin for both base-mediated α-derivatization and subsequent cobalt-catalyzed allylic substitution. The sequential transformations allow for highly

  尽管烯丙基砜具有罕见的1,1-偶极合成子的独特潜力，但很少用于目标导向的合成中，这可能是由于缺乏用于支链选择性烯丙基取代的通用催化方法。在这里，我们确定了烯丙基4-氯苯基砜作为通用介导的碱介导的α-衍生化和随后的钴催化的烯丙基取代。连续转化允许高度区域选择性地获得具有多种脂族侧链的支链烯丙基取代产物。与传统的金属催化方案相比，光氧化还原使能的钴催化对于实现高产率和区域选择性的脱磺酰基取代是必不可少的，而传统的金属催化方案在相应的转化中导致了较差的结果。
• TRANSFER OF ASYMMETRY BY THE PALLADIUM-CATALYZED ALKYLATION OF CHIRAL ALLYLIC SULFINATES
  作者：Kunio Hiroi、Ryuichi Kitayama、Shuko Sato

  DOI：10.1246/cl.1984.929

  日期：1984.6.5

  The palladium-catalyzed substitution of chiral allylic sulfinates was performed by the initial transformation of the sulfinates into allyl sulfones and the subsequent alkylation of the sulfones with retention of configuration. Reaction of trans- and cis-2-butenyl (S)-(−)-p-toluenesulfinate with the sodium salt of dimethyl malonate was undertaken in the presence of tetrakis(triphenylphosphine)palladium and triphenylphosphine to produce dimethyl (S)-(+)- and (R)-(−)-1-buten-3-ylmalonate, respectively, with the α-alkylated product, dimethyl 2-butenylmalonate.

  通过将手性烯丙基亚磺酸盐初步转化为烯丙基磺酸盐，并随后对磺酸盐进行保持构型的烷基化，进行了钯催化的取代反应。以反式和顺式2-丁烯基(S)-(−)-对甲苯磺酸盐与二甲基恶唑酸钠盐在四配位(triphenylphosphine)palladium和三苯基膦的存在下反应，分别生产出二甲基(S)-(+)-和(R)-(−)-1-丁-3-基恶唑酸酯，以及α-烷基化的产物：二甲基2-丁烯基恶唑酸酯。
• Novel [Ruthenium(substituted‐tetramethylcyclopentadiene) (2‐quinolinecarboxylato)(allyl)] Hexafluorophosphate Complexes as Efficient Catalysts for Highly Regioselective Nucleophilic Substitution of Aliphatic Allylic Substrates
  作者：Hui‐Jun Zhang、Bernard Demerseman、Loïc Toupet、Zhenfeng Xi、Christian Bruneau

  DOI：10.1002/adsc.200800135

  日期：2008.7.7

  arrangement. Complexes 3a (R=R′=Me) and 3b are involved as precatalysts favoring the formation of branched products in regioselective nucleophilic allylic substitution reactions, starting from ethyl 2-(E)-hexen-1-yl carbonate and chlorohexene as unsymmetrical aliphatic allylic substrates. Phenols, dimethyl malonate, and primary (aniline) and secondary (pyrrolidine, piperidine) amines have been used

  稳定的六氟磷酸盐[钌（R-取代-四甲基环戊二烯）（2-喹啉羧基）（1-R'-取代烯丙基）（R = Me，R'= H，Me，n- Pr，Ph; R = t- Bu， R'= Me）的和[钌（五甲基环戊二烯）（2- quinolinecarboxylato）（1- ñ -propylallyl）]四氟硼酸盐（4'A），作为allylruthenium（IV）配合物，已在一个步骤中合成，由[钌起始（ R-取代的四甲基环戊二烯）三（乙腈）六氟磷酸盐或四氟硼酸盐络合物，喹二酸和烯丙醇。获得了单一的立体异构体，并确定了3b（R = t- Bu，R'= Me）和4'a的X射线单晶结构允许指定一种首选的安排。配合物3a（R = R'= Me）和3b作为预催化剂参与区域选择性亲核烯丙基烯丙基取代反应中支化产物的形成，起始于乙基2- （E） -己烯-1-基碳酸酯和氯己烯作为不对称脂族烯丙基基材。在温和的碱性条