2-cyclohexyl-5-methylene-4,5-dihydrooxazole | 1245124-77-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 2-cyclohexyl-5-methylene-4,5-dihydrooxazole
• 英文别名: 2-cyclohexyl-5-methylidene-4H-1,3-oxazole
• CAS: 1245124-77-9
• 化学式: C₁₀H₁₅NO
• 分子量: 165.235
• InChiKey: HTZHOVBSJXXKHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二氟溴乙酸乙酯 、 2-cyclohexyl-5-methylene-4,5-dihydrooxazole 在 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 sodium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以78%的产率得到ethyl 3-(2-cyclohexyloxazol-5-yl)-2,2-difluoropropanoate
  参考文献：
  名称：

  亚甲基-2-恶唑啉的光氧化还原催化级联自由基加成/芳构化：轻度获得C（sp 3）-二氟-恶唑衍生物

  摘要：

  恶唑是配位化学，天然产物，药物化学和材料科学中的关键结构支架。[1] 因此，近几十年来，具有多种药理和生物学特性的功能化恶唑的合成已成为研究的重点。[2] 二氟亚甲基（CF 2）是一个氧原子的生物等排体，可以显着影响酸度，偶极矩和相邻基团的构象变化。[3] 总之，二氟烷基化的恶唑骨架中二氟亚甲基和恶唑单元的组合可以通过新的生物活性丰富恶唑的多样性。

  DOI：

  10.1016/j.tetlet.2019.151246
• 作为产物：
  描述：

  N-(prop-2-yn-1-yl)cyclohexanecarboxamide 在 [{2-(diphenylphosphino)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene}AuCl] 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 2-cyclohexyl-5-methylene-4,5-dihydrooxazole
  参考文献：
  名称：

  KITPHOS单膦酸酯的亲电金（I）配合物对炔丙基酰胺的高效环烯异构化：对比研究

  摘要：

  基于二苯基和二环己基膦基的KITPHOS单膦酸酯的亲电金（I）配合物催化一系列炔丙基酰胺的5-exo-dig环异构化反应，得到相应的亚烷基恶唑啉；在所有情况下，由二苯基膦基取代的KITPHOS单膦酸酯形成的催化剂的性能均优于其二环己基膦酸酯基以及基于三苯基膦的催化剂，这表明联芳基/联芳基样骨架可能有助于提高催化剂效率。

  DOI：

  10.1021/om1006769

文献信息

• Synthesis of monofluorooxazoles with quaternary C–F centers through photoredox-catalyzed radical addition of methylene-2-oxazolines
  作者：Gui-Ting Song、Chuan-Hua Qu、Jin-Hong Chen、Zhi-Gang Xu、Cheng-He Zhou、Zhong-Zhu Chen

  DOI：10.1039/d0ob00267d

  日期：——

  A photoredox-catalyzed radical addition of methylene-2-oxazolines has been developed under visible light irradiation to synthesize monofluorooxazoles with quaternary C–F centers using 2-bromo-2-fluoro-3-oxo-3-phenylpropionates as radical source.

  已开发出一种光氧化还原催化的甲亚甲基-2-噁唑烯的自由基加成反应，通过可见光照射合成含季碳-氟中心的单氟噁唑，使用2-溴-2-氟-3-氧代-3-苯丙酸酯作为自由基源。
• Efficient Cycloisomerization of Propargyl Amides by Electrophilic Gold(I) Complexes of KITPHOS Monophosphines: A Comparative Study
  作者：Simon Doherty、Julian G. Knight、A. Stephen K. Hashmi、Catherine H. Smyth、Nicholas A. B. Ward、Katharine J. Robson、Sophie Tweedley、Ross W. Harrington、William Clegg

  DOI：10.1021/om1006769

  日期：2010.9.27

  Electrophilic gold(I) complexes of diphenyl- and dicyclohexylphosphino-based KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of a range of propargyl amides to afford the corresponding alkylidene oxazolines; in all cases catalysts formed from diphenylphosphino-substituted KITPHOS monophosphines outperformed their dicyclohexylphosphino counterparts as well as that based on triphenylphosphine

  基于二苯基和二环己基膦基的KITPHOS单膦酸酯的亲电金（I）配合物催化一系列炔丙基酰胺的5-exo-dig环异构化反应，得到相应的亚烷基恶唑啉；在所有情况下，由二苯基膦基取代的KITPHOS单膦酸酯形成的催化剂的性能均优于其二环己基膦酸酯基以及基于三苯基膦的催化剂，这表明联芳基/联芳基样骨架可能有助于提高催化剂效率。
• Electron Catalytic Photochemical Cascade Carbodifluoroalkylation/Radical Cyclization of Methylene-2-oxazolines
  作者：Chuanhua Qu、Zhongkai Wu、Weipeng Li、Hongbin Du、Chengjian Zhu

  DOI：10.1002/adsc.201700104

  日期：2017.5.17

  electron‐catalyzed, photochemical tandem carbodifluoroalkylation/radical cyclization of enol ethers is disclosed. The reactions occur via addition of difluoroacyl radicals to methylene‐2‐oxazolines and subsequent intramolecular base‐promoted homolytic alkyl substitution (BHAS) of the intermediate oxyl‐alkyl radicals. Initiation of the radical chain reaction is best achieved with a commercially available and cheap

  公开了可操作的绿色的，电子催化的，光化学串联的碳二氟烷基化/烯醇醚的自由基环化。反应是通过在亚甲基-2-恶唑啉中添加二氟酰基基团以及随后的中间羟烷基基团的分子内碱基促进的均质烷基取代（BHAS）来进行的。自由基链反应的引发最好使用可商购获得的廉价有机碱来完成，并且使用容易获得的可见光作为能源。
• Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon–Heteroatom Bond Forming 5-<i>exo</i>-dig and 6-<i>endo</i>-dig Cyclizations
  作者：Simon Doherty、Julian G. Knight、Daniel O. Perry、Nicholas A. B. Ward、Dror M. Bittner、William McFarlane、Corinne Wills、Michael R. Probert

  DOI：10.1021/acs.organomet.6b00146

  日期：2016.5.9

  A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence of increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon-heteroatom bond-forming cyclizations has been investigated. Detailed solution NMR studies on Ph-TRISKITPHOS, its oxide, and the corresponding gold(I) chloride adduct identified a conformational exchange process involving a concerted librational motion of the individual anthracene-derived organic substituents about their P-C bonds. The cessation of this motion at reduced temperatures lowers the molecular symmetry such that the two C6H4 rings in each of the KITPHOS units become inequivalent; a lower energy process involving restricted rotation of the biaryl-like phenyl ring has also been identified. Electrophilic gold(I) complexes of these triaryl-like KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of propargyl amides to afford the corresponding methylene oxazolines, which were used in a subsequent tandem carbonyl-ene reaction to afford functionalized 2 -substituted oxazolines. A comparative survey revealed that catalyst efficiency for cycloisomerization decreases in the order MONOKITPHOS = BISKITPHOS > PPh3 > TRISKITPHOS. The optimum system also catalyzes the selective 6-endo-dig cyclization of 2-alkynylbenzyl alcohols, 2-alkynylbenzoic acid, and 2-phenylethynyl benzamides; gratifyingly, in several cases the yields obtained are markedly higher and/or reaction times significantly shorter than those previously reported for related gold catalysts. Moreover, these are the first examples of gold(I)-catalyzed 6-endo-dig cycloisomerizations involving 2-phenylethynyl benzamides and, reassuringly, the optimum gold(I)/MONOKITPHOS systems either rivaled or outperformed existing silver or palladium based catalysts. The steric parameters of this homologous series of phosphines have been quantified and compared with selected triarylphosphines using a combination of Solid -G calculations, to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%V-bur); the corresponding Tolman cone angles have also been determined from correlations.
• Photoredox catalytic cascade radical addition/aromatization of methylene-2-oxazolines: Mild access to C(sp)-difluoro-oxazole derivatives
  作者：Gui-Ting Song、Chuan-Hua Qu、Jiang-Ping Meng、Zhi-Gang Xu、Cheng-He Zhou、Zhong-Zhu Chen

  DOI：10.1016/j.tetlet.2019.151246

  日期：2019.11

  Oxazoles are pivotal structural scaffolds in coordination chemistry, natural products, medicinal chemistry, and material science.[1] Consequently, the synthesis of functionalized oxazoles with multiple pharmacological and biological properties has become the subject of intense research in recent decades.[2] The difluoromethylene group (CF2), which is a bioisostere for an oxygen atom, can significantly

  恶唑是配位化学，天然产物，药物化学和材料科学中的关键结构支架。[1] 因此，近几十年来，具有多种药理和生物学特性的功能化恶唑的合成已成为研究的重点。[2] 二氟亚甲基（CF 2）是一个氧原子的生物等排体，可以显着影响酸度，偶极矩和相邻基团的构象变化。[3] 总之，二氟烷基化的恶唑骨架中二氟亚甲基和恶唑单元的组合可以通过新的生物活性丰富恶唑的多样性。