2-(but-2-ynyl)-2-(methoxycarbonyl)hex-4-ynoic acid | 1231753-18-6

• 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-(but-2-ynyl)-2-(methoxycarbonyl)hex-4-ynoic acid
• 英文别名: 2-(methoxycarbonyl)-2-(but-2-ynyl)hex-4-ynoic acid；2,2-di(2-butynyl)malonic acid monomethyl ester；2-But-2-ynyl-2-methoxycarbonylhex-4-ynoic acid
• CAS: 1231753-18-6
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: NFMKAAQQSFMVJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(but-2-ynyl)-2-(methoxycarbonyl)hex-4-ynoic acid 在 氢化奎宁 1,4-(2,3-二氮杂萘)二醚 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 正己烷 、 氯仿 为溶剂， 反应 15.25h， 以86%的产率得到(S,E)-methyl 5-(1-bromoethylidene)-3-(but-2-ynyl)-2-oxotetrahydrofuran-3-carboxylate
  参考文献：
  名称：

  Enantioselective, Desymmetrizing Bromolactonization of Alkynes

  摘要：

  Asymmetric bromolactonizations of alkynes are possible using a desymmetrization approach. The commercially available catalyst (DHQD)(2)PHAL promotes these cyclizations in combination with cheap NBS as a bromine source to give bromoenol lactones in high yield and with high enantioselectivity. The bromoenol lactone products, containing a tetrasubstituted alkene and a quaternary stereocenter are valuable building blocks for synthetic chemistry.

  DOI：

  10.1021/ja402910d
• 作为产物：
  描述：

  dimethyl 2,2-di(but-2-yn-1-yl)malonate 在 甲醇 、 potassium hydroxide 作用下， 反应 96.0h， 以74%的产率得到2-(but-2-ynyl)-2-(methoxycarbonyl)hex-4-ynoic acid
  参考文献：
  名称：

  Pd(ii)–SDP-catalyzed enantioselective 5-exo-dig cyclization of γ-alkynoic acids: application to the synthesis of functionalized dihydofuran-2(3H)-ones containing a chiral quaternary carbon center

  摘要：

  介绍了 Pd(II)âSDP 催化的δ,δ-二取代δ-炔酸的首次对映选择性分子内环化。这种 5-exo-dig 环化反应以极好的收率获得了含有手性季碳中心的二氢呋喃-2(3H)-酮，对映选择性高达 71%。提出了一种涉及钯（II）物种的机理，以合理解释反应的结果。

  DOI：

  10.1039/c3ob41103f

文献信息

• An Enantioselective Iodolactonization/Cross-Coupling Protocol for the Synthesis of Highly Substituted Enol Lactones
  作者：Christoph Fricke、Michael Wilking、Constantin G. Daniliuc、Ulrich Hennecke

  DOI：10.1002/ejoc.201800642

  日期：2018.6.29

  A sequence of catalytic enantioselective iodolactonization followed by Palladium‐catalyzed cross‐coupling provides rapid access to highly substituted enol lactones. With DHQD2PHAL as catalyst, moderate to very good enantioselectivities in the iodolactonization step can be obtained.

  一系列的催化对映选择性碘内酯化，然后进行钯催化的交叉偶联，可快速获得高度取代的烯醇内酯。用DHQD 2 PHAL作为催化剂，可以在碘内酯化步骤中获得中等到非常好的对映选择性。
• Water-Soluble Gold(I) and Gold(III) Complexes with Sulfonated <i>N</i>-Heterocyclic Carbene Ligands: Synthesis, Characterization, and Application in the Catalytic Cycloisomerization of γ-Alkynoic Acids into Enol-Lactones
  作者：Eder Tomás-Mendivil、Patrick Y. Toullec、Javier Borge、Salvador Conejero、Véronique Michelet、Victorio Cadierno

  DOI：10.1021/cs4009144

  日期：2013.12.6

  2-pyridyl, 2-picolyl, and 2-pyridylethyl substituents have been synthesized and employed as precursors for the preparation of novel water-soluble Au(I)- and Au(III)-NHC complexes of general composition [AuCl(NHC)] and [AuCl3(NHC)] (NHC = N-heterocyclic carbene), respectively. These complexes proved to be active, selective, and recyclable catalysts for the intramolecular cyclization of γ-alkynoic acids under

  合成了带有3-磺酰基丙基，2-吡啶基，2-吡啶基和2-吡啶基乙基取代基的两性离子咪唑鎓盐，并将其用作制备新型水溶性Au（I）-和Au（III）-NHC配合物的前体组成[AuCl（NHC）]和[AuCl 3（NHC）]（NHC = N-杂环卡宾）。这些络合物被证明是在双相甲苯/水条件下用于γ-链烷酸分子内环化的活性，选择性和可回收催化剂，从而在温和条件下（rt）以高收率得到所需的烯醇内酯。值得注意的是，尽管众所周知金络合物具有促进C≡C键水合的能力，但即使在1,6-二炔的环异构化反应过程中也未观察到竞争水合过程。
• Pd(ii)–SDP-catalyzed enantioselective 5-exo-dig cyclization of γ-alkynoic acids: application to the synthesis of functionalized dihydofuran-2(3H)-ones containing a chiral quaternary carbon center
  作者：Vellaisamy Sridharan、Lulu Fan、Shinobu Takizawa、Takeyuki Suzuki、Hiroaki Sasai

  DOI：10.1039/c3ob41103f

  日期：——

  The Pd(II)–SDP-catalyzed first enantioselective intramolecular cyclization of α,α-disubstituted γ-alkynoic acids is described. This 5-exo-dig cyclization afforded dihydrofuran-2(3H)-ones bearing a chiral quaternary carbon center in excellent yields with enantioselectivities up to 71%. A mechanism involving palladium(II) species is proposed to rationalize the outcome of the reaction.

  介绍了 Pd(II)âSDP 催化的δ,δ-二取代δ-炔酸的首次对映选择性分子内环化。这种 5-exo-dig 环化反应以极好的收率获得了含有手性季碳中心的二氢呋喃-2(3H)-酮，对映选择性高达 71%。提出了一种涉及钯（II）物种的机理，以合理解释反应的结果。
• Sol-Gel Immobilized N-Heterocyclic Carbene Gold Complex as a Recyclable Catalyst for the Rearrangement of Allylic Esters and the Cycloisomerization of γ-Alkynoic Acids
  作者：Meritxell Ferré、Xavier Cattoën、Michel Wong Chi Man、Roser Pleixats

  DOI：10.1002/cctc.201600632

  日期：2016.9.7

  The synthesis of a bis‐silylated (NHC)AuCl (NHC=N‐heterocyclic carbene) complex and the formation of a hybrid silica material by the sol–gel process by cogelification with tetraethylorthosilicate under fluoride catalysis are described. This material was characterized by using 29Si solid‐state NMR spectroscopy, N2 sorption measurements, electron microscopy, and elemental analysis. It was tested as a

  描述了双硅烷化（NHC）AuCl（NHC = N-杂环卡宾）配合物的合成，以及在氟化物催化下与原硅酸四乙酯共凝胶化通过溶胶-凝胶法形成的杂化二氧化硅材料。通过使用29 Si固态NMR光谱N 2对该材料进行了表征吸附测量，电子显微镜和元素分析。在微波条件下，它与银盐一起用于烯丙基酯与银盐的重排中作为可重复使用的催化剂进行了测试，它的性能比均相类似物好得多。该催化剂在室温下在两种反应介质（甲苯/水两相系统和深共熔溶剂）中，将γ-链烷酸环化为五元烯醇-内酯时具有活性且可循环利用。
• Gold-Catalyzed Tandem Cyclizations of 1,6-Diynes Triggered by Internal N- and O-Nucleophiles
  作者：Christian A. Sperger、Anne Fiksdahl

  DOI：10.1021/jo100712d

  日期：2010.7.2

  Investigations on gold-catalyzed tandem cyclization reactions of 1,6-diynes, tethered to nucleophilic functionalities such as amine, carboxylic acid, amide, and sulfonamide, are reported. The ability of such substrates to undergo tandem cyclization, triggered by internal nucleophiles, has been examined. Depending on the substrate, the catalytic system, and reaction conditions, different regioisomers of monocyclic and bridged bicyclic products were obtained.