4-(2-butynyl)-cyclohex-2-en-1-one | 210172-04-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(2-butynyl)-cyclohex-2-en-1-one
• 英文别名: 4-(but-2-ynyl)cyclohex-2-enone；4-(2-butynyl)-2-cyclohexenone；4-But-2-ynylcyclohex-2-en-1-one；4-but-2-ynylcyclohex-2-en-1-one
• CAS: 210172-04-6
• 化学式: C₁₀H₁₂O
• 分子量: 148.205
• InChiKey: CUFFBCFTVDPGPM-UHFFFAOYSA-N

物化性质

• 沸点：
  253.3±19.0 °C(Predicted)
• 密度：
  0.987±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(2-butynyl)-cyclohex-2-en-1-one 在 L-Selectride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以38%的产率得到4-(2-butynyl)cyclohexanone
  参考文献：
  名称：

  Cyclization of Nonterminal Alkynic β-Keto Esters Catalyzed by Gold(I) Complex with a Semihollow, End-Capped Triethynylphosphine Ligand

  摘要：

  A cationic gold(l) complex with a semihollow-shaped trialkynylphosphine catalyzed 5-exo-dig and 6-endo-dig cyclizations of various internal alkynic beta-keto esters, showing a marked advantage over a gold(I)-PPh3 complex with respect to the rates of the reactions and the product yields. It is proposed that the gold-bound alkynic substrate in a catalytic pocket must be somewhat folded and that such a steric effect makes the carbon-carbon bond formation entropically more favorable.

  DOI：

  10.1021/ol802079r
• 作为产物：
  描述：

  3-乙氧基-6-(丙-2-炔-1-基)环己-2-烯酮 在 copper(l) iodide 、 lithium aluminium tetrahydride 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 4-(2-butynyl)-cyclohex-2-en-1-one
  参考文献：
  名称：

  通过路易斯酸促进环状2,6-烯醇的碳卤化反应方便地合成（E）-5-芳基（卤）亚甲基双环-[[2.2.2]辛-2-烯和-[2.2.1]庚-2-烯

  摘要：

  AbstractAn efficient synthesis of (E)‐5‐aryl(halo)methylenebicyclo[2.2.2]oct‐2‐enes is reported. Lewis acid‐promoted carbohalogenation of 4‐(3‐arylprop‐2‐ynyl)‐cyclohex‐2‐enols in dichloromethane proceeds rapidly to afford the exo‐methylene‐bridged bicycles in good yields. This method also provides an easy access to (E)‐5‐aryl(halo)methylenebicyclo[2.2.1]hept‐2‐enes from the five‐membered ring 2,6‐enynols. The reactions are procedurally simple and high yielding, producing the aryl(halo)methylene‐bridged bicycles in minutes under air and mild conditions.magnified image

  DOI：

  10.1002/adsc.201400671

文献信息

• Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex:  Efficient and General Trans Addition
  作者：Barry M. Trost、Zachary T. Ball

  DOI：10.1021/ja0528580

  日期：2005.12.1

  The complex [Cp*Ru(MeCN)3]PF6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to alpha-vinylsilane products with good regioselectivity. Deuterium labeling studies indicate a clean trans addition process is at work. The same complex is active in internal alkyne hydrosilylation, where absolute selectivity for the trans addition process is maintained

  复合物 [Cp*Ru(MeCN)3]PF6 显示可催化多种炔烃的氢化硅烷化。末端炔烃可以提供具有良好区域选择性的 α-乙烯基硅烷产品。氘标记研究表明，清洁的反式添加过程正在发挥作用。相同的复合物在内部炔烃氢化硅烷化中具有活性，其中保持了反式加成过程的绝对选择性。几种内部炔烃底物类别，包括炔丙醇和 α,β-炔基羰基化合物，允许区域选择性乙烯基硅烷的形成。多种硅烷的耐受性值得注意，包括烷基硅烷、芳基硅烷、烷氧基硅烷和卤代硅烷。这种优势在用于硅系分子内 Diels-Alder 环加成反应的三烯底物的直接合成中得到了证明。
• Copper-Catalyzed Cross-Coupling of Vinylsiloxanes with Bromoalkynes: Synthesis of Enynes
  作者：Loïc Cornelissen、Maxime Lefrancq、Olivier Riant

  DOI：10.1021/ol501140p

  日期：2014.6.6

  of various sensitive enynes. The use of cis, trans, and 1,1′-disubstituted vinylsiloxanes was allowed, and full retention of stereochemistry was observed. Sensitive groups such as halides, unsaturated ketones, and aldehydes were fully tolerated.

  烯炔是有机合成中的多功能构建基块。呈现了铜催化的乙烯基硅氧烷与溴代炔烃的Hiyama型交叉偶联。这种温和而有效的方法导致形成各种敏感的烯炔。允许使用顺式，反式和1,1'-二取代的乙烯基硅氧烷，并且观察到立体化学的完全保留。诸如卤化物，不饱和酮和醛等敏感基团是完全可耐受的。
• Copper-Catalyzed Vinylsilane Allylation
  作者：Loïc Cornelissen、Sébastien Vercruysse、Ayoub Sanhadji、Olivier Riant

  DOI：10.1002/ejoc.201301360

  日期：2014.1

  compounds. Hereby, we describe a new copper-catalyzed vinylsilane transformation. Various vinylsilanes were allylated by using a copper(I) salt, and this led to the formation of polysubstituted 1,4-dienes bearing sensitive moieties such as halogens, ketones, and aldehydes. Hereby is described a new copper-catalyzed vinylsilane transformation. Various vinylsilanes were allylated by using copper(I) salts

  软反应条件，在全合成中尤为重要，已将许多研究人员拖入甲硅烷基化有机化合物领域。因此，我们描述了一种新的铜催化乙烯基硅烷转化。各种乙烯基硅烷通过使用铜 (I) 盐进行烯丙基化，这导致形成带有敏感部分（如卤素、酮和醛）的多取代 1,4-二烯。在此描述了一种新的铜催化乙烯基硅烷转化。各种乙烯基硅烷通过使用铜 (I) 盐进行烯丙基化，这导致形成带有敏感部分（如卤素、酮和醛）的多取代 1,4-二烯。TBAT = 四丁基二氟三苯基硅酸铵。版权所有 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim。
• Reductive cyclization of α-cyclopropylketones with alkynyl- and aryl-tethered substituents
  作者：Maurizio Fagnoni、Philip Schmoldt、Thorsten Kirschberg、Jochen Mattay

  DOI：10.1016/s0040-4020(98)00323-8

  日期：1998.6

  Photoinduced electron transfer (PET) reactions of α-cyclopropyl-substituted ketones and triethylamine (TEA) were used to initiate the cyclopropylcarbinyl-homoallyl rearrangement. The intramolecular cyclization reaction onto triple bonds was performed yielding bicyclic and spirocyclic compounds. Furthermore, in some preliminary studies it was shown that even intramolecular aromatic substitutions are

  α-环丙基取代的酮与三乙胺（TEA）的光诱导电子转移（PET）反应用于引发环丙基羰基-高烯丙基重排。进行到三键上的分子内环化反应，得到双环和螺环化合物。此外，在一些初步研究中表明，甚至分子内芳族取代也是可行的。
• Gold-Catalyzed Cyclizations of Alkynyl Silyl Enol Ethers: An Easy Access to Bicyclo[3.2.1]octanone Derivatives
  作者：Amandine Carrër、Christophe Péan、Françoise Perron-Sierra、Olivier Mirguet、Véronique Michelet

  DOI：10.1002/adsc.201501135

  日期：2016.4.28

  efficient gold‐catalyzed cyclization reactions of alkynyl silyl enol ethers were successfully applied to the preparation of bicyclo[3.2.1]octanone derivatives. Accordingly, after optimization of the gold catalytic system, several bicyclic α,β‐unsaturated keto adducts were synthesized in good to excellent yields. The process followed a major 5‐exo cyclization via an anti addition of the silyl enol ether to

  炔基甲硅烷基烯醇醚的金催化高效环化反应已成功地用于制备双环[3.2.1]辛酮衍生物。因此，在优化金催化体系后，合成了几种双环α，β-不饱和酮加合物，收率良好至极佳。所遵循的过程的主要5-外型环化通过一个反加成的甲硅烷基烯醇醚的π共活化的中间体，将其通过一个氘掺入实验证实。甲6-内观察到甲硅烷基烯醇醚轴承供电子芳族基团的环化过程。