(Z)-2-(trifluoromethanesulfonyloxymethylene)cyclopentanone | 134251-47-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (Z)-2-(trifluoromethanesulfonyloxymethylene)cyclopentanone
• 英文别名: (Z)-(2-oxocyclopentylidene)methyl trifluoromethanesulfonate；[(Z)-(2-oxocyclopentylidene)methyl] trifluoromethanesulfonate
• CAS: 134251-47-1
• 化学式: C₇H₇F₃O₄S
• 分子量: 244.191
• InChiKey: PJBOSKBCVPVZQT-PLNGDYQASA-N

物化性质

• 沸点：
  284.6±40.0 °C(Predicted)
• 密度：
  1.670±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-2-(trifluoromethanesulfonyloxymethylene)cyclopentanone 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 正丁基锂 、 二异丙胺 、 六甲基二硅氮烷 作用下， 反应 4.58h， 生成 (Z)-5-(3-trimethylsilyl-2-propynylidene)-1-cyclopenten-1-yl trifluoromethanesulfonate
  参考文献：
  名称：

  Scheuplein, Stefan W.; Harms, Klaus; Brueckner, Reinhard, Chemische Berichte, 1992, vol. 125, # 1, p. 271 - 278

  摘要：

  DOI：
• 作为产物：
  描述：

  2-氧代环戊烷-1-甲醛 在 2,6-二叔丁基-4-甲基吡啶 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 1.67h， 生成 (Z)-2-(trifluoromethanesulfonyloxymethylene)cyclopentanone
  参考文献：
  名称：

  与新carcarinostatin发色团有关的化合物的合成研究。2.开链（E）-和（Z）-二烯二炔体系的合成及其在菌株释放的环状类似物合成中的应用

  摘要：

  “双耦合”（的反应ë） -和（Ž（）-dienol ditriflates 5和6）与各种炔丙醇被发现，得到（ë） -和（Ž）-dienediyne二醇，开链类似物碳素抑制素生色团的立体定位。这些（E）-和（Z）-二烯二炔二醇对P388鼠类白血病表现出可比的细胞毒性。的“单耦合”反应6发生优先在所述外-环位置得到单烯醇三氟甲磺酸酯，其可以通过与乙炔的第二次偶联反应进一步加工成二烯二炔化合物。该合成方案的应用可以提供新颖的，可释放应变的环状二烯二炔乙缩醛（33）。

  DOI：

  10.1016/s0040-4020(01)92247-1

文献信息

• A Versatile and Highly Stereoselective Access to Vinyl Triflates Derived from 1,3-Dicarbonyl and Related Compounds
  作者：Simon Specklin、Philippe Bertus、Jean-Marc Weibel、Patrick Pale

  DOI：10.1021/jo8015049

  日期：2008.10.3

  trialkylamines or DBU followed by trapping with triflic anhydride probably accounted for such high selectivity, achieved even at 0 degrees C. This method offers the first direct route to vinyl triflates from beta-ketoamides, beta-ketophosphonates and beta-ketosulfones.

  1,3-二羰基衍生物，例如1,3-二酮，β-酮醛，β-酮酸酯，β-酮酰胺，β-酮膦酸酯和β-酮砜被高效地转化为相应的具有高立体选择性的Z乙烯基三氟甲磺酸酯。在二氯甲烷中用三氟甲磺酸锂进行预配位，然后用温和的碱（例如三烷基胺或DBU）进行烯化，然后用三氟甲磺酸酐进行捕获，可能导致如此高的选择性，即使在0摄氏度下也是如此。这种方法为从β-酮酰胺制得三氟甲磺酸三氟甲磺酸酯提供了第一条直接途径，β-酮膦酸酯和β-酮砜。
• Synthesis of enynes related to neocarzinostatine using the new catalyzed coupling reaction
  作者：P. Bertus、P. Pale

  DOI：10.1016/s0040-4039(97)10253-2

  日期：1997.11

  Both E and Z isomers of 2-triflyloxymethylene cyclopentanone, 1 and 2 respectively, have been coupled with various functionalized acetylenes in the presence of the set of catalysts. This method provides a rapid and stereoselective access to various E or Z 2-(alkynyl)methylene cyclopentanone derivatives, which are promising and versatile intermediates toward NCS-Chrom and analogs.

  在该组催化剂的存在下，分别将2-三氟乙氧基环戊酮的E和Z异构体1和2与各种官能化的乙炔偶联。该方法提供了对各种E或Z 2-（炔基）亚甲基环戊酮衍生物的快速立体选择，这是对NCS-Chrom及其类似物的有前途的通用中间体。
• Synthesis of enynes and epoxyenynes by coupling: use of a new set of catalysts based on Pd–Ag salts
  作者：Philippe Bertus、Patrick Pale

  DOI：10.1016/s0022-328x(98)00681-0

  日期：1998.9

  The new couple of catalysts Pd(PPh3)(4) and AgI are very efficient for the coupling of vinyltriflates and terminal alkynes in the presence of a bulky amine in dimethylformamide at room temperature. Enynes and epoxyenynes are obtained in good to excellent yields. As illustrated with several examples, a wide variety of functional groups are well tolerated in the described conditions. Silver acetylides have been proposed as intermediate in this reaction. (C) 1998 Elsevier Science S.A. All rights reserved.
• Scope and Facial Selectivity of the Prins-Pinacol Synthesis of Attached Rings
  作者：Larry E. Overman、Emile J. Velthuisen

  DOI：10.1021/jo0522862

  日期：2006.2.1

  [GRAPHICS]Using a B-alkyl Suzuki cross-coupling as a key step, a concise and stereocontrolled synthesis of five- to eight-membered triisopropylsiloxy ethers having (2Z)-(6,6-dimethoxyhexylidene) or (2Z)-(5,5-dimethoxypentylidene) side chains was developed. Prins-pinacol reactions of these precursors promoted by SnCl4 provide bicyclic products in which 5-, 6-, or 7-membered rings are joined by a C-C single bond. Synthetically challenging attached ring systems in which both rings are chiral can be prepared in this fashion with high stereo- and enantioselectivity. Stabilizing through-space electrostatic interactions between the alpha-alkoxycarbenium ion and an axially positioned oxygen substituent are believed to play a significant role in organizing the transition structure of the Prins cyclization.
• Rapid and stereoselective construction of dienediynes related to the neocarzinostatin chromophore
  作者：Reinhard Brückner、Stefan W. Scheuplein、Jean Suffert

  DOI：10.1016/0040-4039(91)80355-a

  日期：1991.3

  Formylcyclopentanone was transformed into Z configuration dienediynes 15 in three steps. As the key step served Pd catalyzed stereoselective couplings of the isomerically pure bis(enoltriflate) 13 with two equiv. of alkyne.