dimethyl 2-ethynylcyclopropane-1,1-dicarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 2-ethynylcyclopropane-1,1-dicarboxylate
• 英文别名: 1,1-Dimethyl 2-ethynylcyclopropane-1,1-dicarboxylate
• 化学式: C₉H₁₀O₄
• 分子量: 182.176
• InChiKey: MQQNVEHPJXDXMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  4
• 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：

  dimethyl 2-ethynylcyclopropane-1,1-dicarboxylate 在 bis-triphenylphosphine-palladium(II) chloride 、 20% palladium hydroxide-activated charcoal 、 氢气 、 三乙胺 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙酸乙酯 、 甲苯 为溶剂， 20.0~60.0 ℃ 、101.33 kPa 条件下， 反应 2.17h， 生成 dimethyl 11-benzyl-5,7,8,10-tetrahydro-7,10-epiminocycloocta[c]pyridine-9,9(6H)-dicarboxylate
  参考文献：
  名称：

  通过分子内交叉[3 + 2]环加成策略合成（-）-吡啶基[3,4-b]高环烷（PHT）和（±）-PHT

  摘要：

  从便利的起始原料开始，通过7个步骤即可有效合成（-）-吡啶基[3,4- b ]高环烷（PHT）和（±）-PHT。关键的转变包括通过Sc（OTf）3催化的分子内跨[3 + 2]环加成（IMCC），然后进行Krapcho脱羧和Barton还原脱羧，有效构建9-氮杂-[4.2.1]壬桥核心骨架。本工作为合成其他桥接类似物提供了一种通用而有效的策略。

  DOI：

  10.1002/adsc.201701438
• 作为产物：
  描述：

  dimethyl 2-(3,3-diphenyl-3-(trimethylsilyl)prop-1-ynyl)cyclopropane-1,1-dicarboxylate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以88%的产率得到dimethyl 2-ethynylcyclopropane-1,1-dicarboxylate
  参考文献：
  名称：

  Synthesis of Enantioenriched Allenes from 1,1-Cyclopropanediesters

  摘要：

  Highly substituted allenes were obtained by the S(N)2' addition of organocuprate reagents on 2-propargyl-1,1-cyclopropanediesters. This new methodology permits the synthesis of highly enantioenriched allenes as the reaction proceeds with retention of the enantiomeric purity of the starting cyclopropane. The use of higher order cuprates was instrumental in obtaining the reported results.

  DOI：

  10.1021/ol902766f

文献信息

• Iron-catalyzed addition of Grignard reagents to activated vinyl cyclopropanes
  作者：Benjamin D. Sherry、Alois Fürstner

  DOI：10.1039/b918818e

  日期：——

  A highly regioselective iron-catalyzed addition of branched primary, secondary or tertiary alkyl Grignard reagents to activated vinyl cyclopropanes is described, which likely proceeds by a direct addition mechanism as opposed to single electron transfer or an iron-allyl based process.

  描述了高区域选择性的铁催化的支链伯，仲或叔烷基格氏试剂向活化的乙烯基环丙烷的加成反应，其可能通过直接加成机理而不是单电子转移或基于铁-烯丙基的方法进行。
• Lewis Acid Catalyzed Intramolecular [3 + 2] Cross Cycloadditions of Cobalt-Alkynylcyclopropane 1,1-Diesters with Carbonyls for Construction of Medium-Sized and Polycyclic Skeletons
  作者：Junhui Zhang、Siyang Xing、Jun Ren、Shende Jiang、Zhongwen Wang

  DOI：10.1021/ol503285u

  日期：2015.1.16

  A Lewis acid catalyzed intramolecular [3 + 2] cross cycloaddition of cobalt-alkynylcyclopropane 1,1-diesters with carbonyls has been successfully developed. Together with simple and efficient postcycloadditions of the cobalt-alkyne moiety, a general and efficient strategy for construction of structurally complex and diverse medium-sized skeletons and related polycycles was supplied successfully.

  已经成功开发了路易斯酸催化的钴-炔基环丙烷1,1-二酯与羰基的分子内[3 + 2]交叉环加成反应。连同钴炔基部分的简单有效的环加成反应，成功地提供了构建结构复杂多样的中型骨架和相​​关多环的通用有效策略。
• Radical Addition of Dimethyl 2‐Ethynylcyclopropane‐1,1‐dicarboxylate to Electron‐Rich Olefins
  作者：Jeffrey H. Byers、Peter H. Goff、Nicholas J. Janson、Michael G. Mazzotta、John E. Swigor

  DOI：10.1080/00397910701319163

  日期：2007.6.1

  Abstract The phenylseleno radical–catalyzed addition of dimethyl 2‐ethynylcyclopropane‐1,1‐dicarboxylate to electron–rich olefins has been achieved. This radical process leads to formation of highly substituted ethynylcyclopentane products through a [3+2] annulation.

  摘要 苯硒基催化 2-乙炔基环丙烷-1,1-二羧酸二甲酯与富电子烯烃的加成反应已经实现。这种自由基过程导致通过 [3+2] 环化形成高度取代的乙炔基环戊烷产物。
• Ruthenium-Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates
  作者：Yoshihiro Miyake、Satoshi Endo、Taichi Moriyama、Ken Sakata、Yoshiaki Nishibayashi

  DOI：10.1002/anie.201207801

  日期：2013.2.4

  It's complex: Ruthenium‐catalyzed [3+2] cycloaddition of ethynylcyclopropanes with aldehydes and aldimines has been found to give the corresponding 2‐ethynyltetrahydrofurans or ‐pyrrolidines in high to excellent yields. In both cases, the formation of a ruthenium allenylidene complex as a key reactive intermediate is supported by density functional theory calculations. Cp*=η5‐C5Me5.

  它很复杂：发现乙炔基环丙烷与钌和醛亚胺在钌催化的[3 + 2]环加成反应中，可以以高产率或优异产率得到相应的2-乙炔基四氢呋喃或吡咯烷。在这两种情况下，密度泛函理论计算都支持了钌烯基亚烷基络合物作为关键的反应性中间体的形成。的Cp * =η 5 -C 5我5。
• Novel formation and use of a Nicholas carbocation in the synthesis of highly substituted tetrahydrofurans
  作者：Steven D. R. Christie、Ryan J. Davoile、Mark R. J. Elsegood、Ross Fryatt、Raymond C. F. Jones、Gareth J. Pritchard

  DOI：10.1039/b411367e

  日期：——

  The first formation of a Nicholas carbocation through cleavage of a carbon-carbon sigma bond has allowed the preparation of highly substituted tetrahydrofurans in a formal dipolar cycloaddition reaction.

  通过裂解碳-碳西格玛键的第一个尼古拉斯碳正离子的形成，可以在正式的偶极环加成反应中制备高度取代的四氢呋喃。