dimethyl 2-(2-oxoethyl)-2-(prop-2-yn-1-yl)malonate | 352664-56-3

• 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-(2-oxoethyl)-2-(prop-2-yn-1-yl)malonate
• 英文别名: dimethyl 2-(2-oxoethyl)-2-(prop-2-ynyl)malonate；3,3-bis(methoxycarbonyl)-5-hexyn-1-al；3,3-di(methoxycarbonyl)-5-hexyn-1-al；3,3-bis(methoxycarbonyl)-5-hexynal；Dimethyl 2-(2-oxoethyl)-2-prop-2-ynylpropanedioate
• CAS: 352664-56-3
• 化学式: C₁₀H₁₂O₅
• 分子量: 212.202
• InChiKey: RLPLBJYIABYYNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(2-oxoethyl)-2-(prop-2-yn-1-yl)malonate 在 氘代三氟乙酸 作用下， 反应 24.0h， 以70%的产率得到dimethyl 5-oxocyclohex-3-ene-1,1-dicarboxylate-2,2-d2
  参考文献：
  名称：

  Brønsted Acid-Promoted Intramolecular Carbocyclization of Alkynals Leading to Cyclic Enones

  摘要：

  TFA-promoted exo carbocyclizations of nonterminal 7-alkynals gave good to excellent yields of seven-membered cycloalkenones, a medium-sized functionalized ring present in natural products with relevant pharmacological properties. Nonterminal 5- and 6-alkynals also gave very good yields of the corresponding exo cyclopentenones and cyclohexenones. On the other hand, terminal 5-alkynals gave endo carbocyclizations to cyclohexenones. These carbocyclizations can be considered as tandem alkyne hydration/aldol condensation processes.

  DOI：

  10.1021/ol900142r
• 作为产物：
  描述：

  在 高氯酸 作用下， 以 乙腈 为溶剂， 生成 dimethyl 2-(2-oxoethyl)-2-(prop-2-yn-1-yl)malonate
  参考文献：
  名称：

  乙炔硫缩醛一氧化物：某些共轭加成-烷基化反应导致不对称的1,4-二羰基系统

  摘要：

  DOI：

  10.1016/s0040-4039(01)87318-4

文献信息

• Vinyl Dihydropyrans and Dihydrooxazines: Cyclizations of Catalytic Ruthenium Carbenes Derived from Alkynals and Alkynones
  作者：Fermín Cambeiro、Susana López、Jesús A. Varela、Carlos Saá

  DOI：10.1002/anie.201400675

  日期：2014.6.2

  A novel synthesis of 2‐vinyldihydropyrans and dihydro‐1,4‐oxazines (morpholine derivatives) from alkynals and alkynones has been developed. The cyclizations require a mild generation of catalytic ruthenium carbenes from terminal alkynes and (trimethylsilyl)diazomethane followed by trapping with carbonyl nucleophiles. Mechanistic aspects of the new cyclizations are discussed.

  已经开发了由炔烃和炔酮合成2-乙烯基二氢吡喃和二氢-1,4-恶嗪（吗啉衍生物）的新方法。环化需要从末端炔烃和（三甲基甲硅烷基）重氮甲烷中轻度生成催化钌碳烯，然后用羰基亲核试剂捕集。讨论了新环化的机械方面。
• Thiyl radical-mediated cyclization of ω-alkynyl O-tert-butyldiphenylsilyloximes
  作者：Nina Shibata、Takahisa Tsuchiya、Yoshimitsu Hashimoto、Nobuyoshi Morita、Shintaro Ban、Osamu Tamura

  DOI：10.1039/c7ob00279c

  日期：——

  thiyl radical to the alkynyl group followed by radical cyclization of the corresponding vinyl radical onto the O-silyloxime moiety to give cyclic O-silylhydroxylamines in good yields. The reactivity of O-silyloximes in radical cyclization was similar to or even higher than that of O-benzyloximes. Facile removal of the silyl group of the cyclization products leading to hydroxylamines and nitrone formation

  ω-炔基O-叔丁基-丁基二苯基甲硅烷基肟，在回流的苯中在偶氮二异丁腈（AIBN）存在下用无味的4-叔丁基苯硫醇处理后，向炔基中添加噻吩基，然后将相应的乙烯基自由基进行自由基环化该Ø -silyloxime部分给循环Ø -silylhydroxylamines良好收益。的反应性Ó在自由基环化-silyloximes物相似或比其还要高Ó -benzyloximes。还证明了容易除去环化产物的甲硅烷基导致羟胺和羟胺的硝酮形成。
• Enantioselective gold(<scp>i</scp>)-catalyzed rearrangement of cyclopropyl-substituted 1,6-enynes into 2-oxocyclobutyl-cyclopentanes
  作者：Zhiyong Wu、David Lebœuf、Pascal Retailleau、Vincent Gandon、Angela Marinetti、Arnaud Voituriez

  DOI：10.1039/c7cc03234j

  日期：——

  A gold(I)-catalyzed cycloisomerization/ring expansion sequence allows the highly enantioselective synthesis of 2-oxocyclobutylcyclopentane derivatives from cyclopropyl-substituted enynes. The bimetallic [(R)-MeO-DTBM-BIPHEP-(AuCl)2] complex was found to be the best precatalyst, affording the desired cyclobutanones in high yields and enantioselectivities (up to 99% ee). The usefulness of the method

  金（I）催化的环异构化/环扩环序列允许由环丙基取代的炔烃高度对映选择性地合成2-氧代环丁基环戊烷衍生物。发现双金属[（R）-MeO-DTBM-BIPHEP-（AuCl）2 ]络合物是最好的预催化剂，以高收率和对映选择性（高达99％ee）提供所需的环丁酮。通过制备russujaponol D的三环核心支架进一步证明了该方法的有效性。
• Synthesis of [2H,13C]-Labelled Diallylmalonates − Useful Probes for the Study of Transition Metal-Catalysed 1,6-Diene Cycloisomerisation
  作者：Katharine L. Bray、Guy C. Lloyd-Jones

  DOI：10.1002/1099-0690(200105)2001:9<1635::aid-ejoc1635>3.0.co;2-c

  日期：2001.5

  Reliable synthetic routes to isotopically labelled dimethyl [13C,2H]diallylmalonates (1) have been developed. Dimethyl diallylmalonates readily undergo transition-metal catalysed cycloisomerisation and the isotopically labelled substrates are expected to be of general utility in the study of the mechanism of such reactions. In the synthetic routes developed, the 2H labelled allyl chains were introduced

  已开发出同位素标记的二甲基 [13C,2H] 二烯丙基丙二酸酯 (1) 的可靠合成路线。二甲基二烯丙基丙二酸酯很容易经历过渡金属催化的环异构化，并且同位素标记的底物有望在此类反应机理的研究中具有普遍用途。在开发的合成路线中，通过使用 Schwartz 试剂还原炔丙基官能团来引入 2H 标记的烯丙基链。这种反应的区域和立体选择性允许高选择性标记策略。使用 [3-13C1] 苯甲酸烯丙酯作为烯丙基亲电试剂，通过 Pd 催化的 13C 或 2H 标记的二甲基烯丙基丙二酸阴离子的烯丙基烷基化引入 13C 标记的烯丙基链。使用这些方法，二甲基 [1,7-(E,E)-2H2]hept-1,6-dienyl-4,4-dicarboxylate (5), 二甲基 [2,
• Reaction of Enol Ethers with Alkynes Catalyzed by Transition Metals: 5exo-dig versus 6endo-dig Cyclizations via Cyclopropyl Platinum or Gold Carbene Complexes
  作者：Cristina Nevado、Diego J. Cárdenas、Antonio M. Echavarren

  DOI：10.1002/chem.200204646

  日期：2003.6.6

  in methanol is catalyzed by electrophilic Pt(II), Pd(II), and Au(III) chlorides and by a Cu(I) complex to give five- or six-membered rings bearing dimethyl acetals. The reaction takes place by an anti addition of the enol ether and the metal to the alkyne. The possible involvement of vinylidene complexes in this reaction is excluded. In addition to the usual 5-exo-dig (or 6-exo-dig) pathways, a 6-endo-dig

  亲电子的Pt（II），Pd（II）和Au（III）氯化物以及Cu（I）络合物催化烯醇醚与炔烃在甲醇中的分子内反应，得到带有二甲基乙缩醛的五元或六元环。通过将烯醇醚和金属抗加成至炔烃中来进行反应。排除了亚乙烯基络合物在该反应中的可能参与。除了通常的5-exo-dig（或6-exo-dig）途径外，还发现某些烯炔还发生6-endo-dig途径。还发现了一种5-endo-dig环化的情况。提出了基于PtCl（2）和AuCl（3）配合物的DFT计算，包括外和内环化的过渡金属催化的炔烃烷氧基环化的一般方案。