N-cyclohexyl-2-(phenylethynyl)benzamide | 1374227-82-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-cyclohexyl-2-(phenylethynyl)benzamide
• CAS: 1374227-82-3
• 化学式: C₂₁H₂₁NO
• 分子量: 303.404
• InChiKey: ANVDXDGHOZHHKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  29.1
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-cyclohexyl-2-(phenylethynyl)benzamide 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 lithium perchlorate 、 三乙胺 、 sodium bromide 作用下， 以 乙腈 为溶剂， 反应 11.0h， 生成 (Z)-N-((E)-3-(1,3-diphenylprop-2-yn-1-ylidene)isobenzofuran-1(3H)-ylidene)cyclohexanamine
  参考文献：
  名称：

  使用邻炔基苯甲酰胺的氧化卤环化电化学合成异苯并呋喃-1-亚胺

  摘要：

  在温和的反应条件下，使用容易获得的 NaX（X = Cl、Br 和 I）盐实现了o-炔基苯甲酰胺的电化学氧化 5 -exo-dig -oxo-halocyclization 。使用廉价且高度稳定的卤化钠作为卤化物离子源对于合成各种卤代异苯并呋喃-1-亚胺是令人印象深刻的。该电化学方案在不使用化学计量的氧化剂和过渡金属催化剂的情况下以良好的收率显示出区域选择性和向异苯并呋喃-1-亚胺的出色转化。

  DOI：

  10.1039/d1ob00953b
• 作为产物：
  描述：

  2-碘苯甲酸 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 草酰氯 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 4.33h， 生成 N-cyclohexyl-2-(phenylethynyl)benzamide
  参考文献：
  名称：

  饱和酰胺/胺的邻炔化衍生物的电化学还原级联环化

  摘要：

  通过电解下的质子耦合电子转移（PCET）实现了邻炔基化衍生物前所未有的还原氢酰胺化/氢喹唑啉级联环化。通过电解，通过酰胺基/喹唑啉酮氨基自由基与 C-C 三键加成，通过 5-exo-dig 环化，然后进行烯属还原，一步完成异吲哚酮和新型异吲哚稠合喹唑啉酮的快速组装，无需外部还原剂。控制和循环伏安实验支持电化学级联的机械解释，这些实验表明电解质是烯烃还原的氢源。

  DOI：

  10.1039/d3cc03350c

文献信息

• Synthesis of 1,3-Dihydrobenzo[c]thiophene-imines via Tandem Reactions of o-(1-Alkynyl)benzamides and Lawesson's Reagent
  作者：Qiuping Ding、Yiyuan Peng、Xianjin Liu、Hongming Wang、Min Chen

  DOI：10.1055/s-0031-1289722

  日期：2012.3

  Metal-free, one-pot tandem reactions of o-(1-alkyn­yl)benzamides proceed smoothly in the presence of Lawesson’s reagent­ leading to 1,3-dihydrobenzo[c]thiophene-imine derivatives in moderate to excellent yields under mild conditions. The method is highly regiospecific for the o-(1-alkynyl)benzothioamide, and only the five-membered-ring product is generated via a 5-exo-dig cyclization involving the

  在Lawesson试剂的存在下，o-（1-炔基）苯甲酰胺的无金属单锅串联反应可顺利进行，从而在温和的条件下以中等至极好的收率得到1,3-二氢苯并[ c ]噻吩-亚胺衍生物。该方法对邻-（1-炔基）苯并硫代酰胺具有高度的区域特异性，并且通过涉及硫原子的5- exo- dig环化仅生成五元环产物。 邻-（1-炔基）苯并硫代酰胺-串联反应-Lawesson试剂-无金属-杂环
• Controlled Photochemical Synthesis of Substituted Isoquinoline-1,3,4(2<i>H</i>)-triones, 3-Hydroxyisoindolin-1-ones, and Phthalimides via Amidyl Radical Cyclization Cascade
  作者：Mandapati Bhargava Reddy、Kesavan Prasanth、Ramasamy Anandhan

  DOI：10.1021/acs.orglett.2c01296

  日期：2022.5.27

  We report a controlled radical cyclization cascade of isoquinoline-1,3,4(2H)-triones, 3-hydroxyisoindolin-1-ones, and phthalimides from o-alkynylated benzamides by metal-free photoredox catalyzed amidyl N-centered radical addition to the C–C triple bond using the proton-coupled electron transfer (PCET) process under mild reaction conditions. A time tunable synthesis of 3-hydroxyisoindolin-1-ones and

  我们报告了异喹啉-1,3,4( 2H )-三酮、3-羟基异吲哚啉-1-酮和邻苯二甲酰亚胺的可控自由基环化级联反应，通过无金属光氧化还原催化的酰胺基 N 中心自由基加成在温和的反应条件下，使用质子耦合电子转移 (PCET) 过程形成 C-C 三键。在可见光照射下，还实现了通过 β-羰基-C(sp 3 ) 键断裂合成 3-羟基异吲哚啉-1-酮和邻苯二甲酰亚胺的时间可调合成。各种控制和淬火实验以及 EPR 研究支持自由基环化级联的机械原理。
• 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.