N-(2-iodobenzyl)-N,3-diphenylpropiolamide | 1364231-68-4

• 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-(2-iodobenzyl)-N,3-diphenylpropiolamide
• 英文别名: N-[(2-iodophenyl)methyl]-N,3-diphenylprop-2-ynamide
• CAS: 1364231-68-4
• 化学式: C₂₂H₁₆INO
• 分子量: 437.28
• InChiKey: BYEGSOKRLXPORG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2-iodobenzyl)-N,3-diphenylpropiolamide 在 bis-triphenylphosphine-palladium(II) chloride 、 N-碘代丁二酰亚胺 、 四丁基溴化铵 、 水 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 120.0 ℃ 、101.33 kPa 条件下， 反应 23.0h， 生成 6-iodo-5-phenyl-1H-pyrrolo[2,1-e]phenanthridine-2,7-(9H,13bH)-dione
  参考文献：
  名称：

  Intramolecular ipso-Halocyclization of 4-(p-Unsubstituted-aryl)-1-alkynes Leading to Spiro[4,5]trienones: Scope, Application, and Mechanistic Investigations

  摘要：

  A new, general method for the synthesis of spiro[4,5]trienores is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the O-18-labeling experiments and DFT calculations.

  DOI：

  10.1021/jo300037n
• 作为产物：
  描述：

  2-碘苯甲醛 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 10.0h， 生成 N-(2-iodobenzyl)-N,3-diphenylpropiolamide
  参考文献：
  名称：

  通过氨基到烷基 1,5-钯迁移结合分子内 C(sp3)–C(sp2) 偶联快速获得稠合四环 N-杂环

  摘要：

  通过钯催化异氰化物与炔系芳基碘化物的环化，提出了一种前所未有的制备稠合四环N-杂环的路线。在此转化中，首先观察到一种新的氨基到烷基1,5-钯迁移/分子内C(sp 3 )–C(sp 2 )偶联序列。更重要的是，异氰化物表现出三种作用，同时充当C1合成子、C1N1合成子和C(sp 3 ) –C (sp 2 )偶联的C ( sp 3 )供体，并且该反应是唯一成功的例子实现了异氰化物的C(sp 3 )–H活化。

  DOI：

  10.1021/acs.orglett.3c02034

文献信息

• Transformations of N-arylpropiolamides to indoline-2,3-diones and acids via C≡C triple bond oxidative cleavage and C(sp2)–H functionalization
  作者：Ming-Bo Zhou、Yang Li、Xuan-Hui Ouyang、Jin-Heng Li

  DOI：10.1007/s11426-019-9633-x

  日期：2020.2

  A new palladium-catalyzed oxidative conversion of N-arylpropiolamides and H2O to various indoline-2,3-diones and acids through the C≡C triple bond cleavage and C(sp2)–H functionalization is described, which is promoted by a cooperative action of catalytic CuBr2, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and O2. The method provides a practical tool for transformations of alkynes by means of a C–H

  描述了通过C tripleC三键裂解和C（sp 2）-H官能化作用，将新的钯催化的N-芳基丙酰胺和H 2 O氧化转化为各种二氢吲哚-2,3-二酮和酸的过程，这一点受到促进。催化的CuBr的协作动作2，2,2,6,6-四甲基-1-哌啶氧（TEMPO）和O 2。该方法通过C–H官能化策略为炔烃的转化提供了实用的工具，该方法可在单个反应中形成一个C–C键和多个C–O键，并具有高的底物相容性和出色的官能团耐受性。
• Synthesis of 3,4-Fused Tricyclic Indoles through Cascade Carbopalladation and C–H Amination: Development and Total Synthesis of Rucaparib
  作者：Cang Cheng、Xiang Zuo、Dongdong Tu、Bin Wan、Yanghui Zhang

  DOI：10.1021/acs.orglett.0c01513

  日期：2020.7.2

  3,4-Fused tricyclic indole scaffolds are ubiquitous in bioactive natural products and pharmaceuticals. A new protocol for the synthesis of 3,4-fused tricyclic indoles has been developed through cascade carbopalladation and C–H amination with N,N-di-tert-butyldiaziridinone. The protocol allows access to a range of 3,4-fused tricyclic indoles, including those containing various linkers and fused with

  3,4-融合的三环吲哚支架在生物活性天然产物和药物中普遍存在。通过级联碳氢键合和N，N-二叔丁基二氮杂吡啶酮的CH-H胺化反应，已开发出一种新的3,4-稠合三环吲哚合成方法。该协议允许访问一系列3,4-稠合的三环吲哚，包括那些包含各种接头并与中等大小的环稠合的吲哚。Rucaparib可以通过该反应合成，为FDA批准的癌症药物提供了一种有利的合成方法。
• Palladium-Catalyzed <i>anti</i>-Carbosilylation of Alkynes to Access Isoquinolinone-Containing Exocyclic Vinylsilanes
  作者：Cang Cheng、Yanghui Zhang

  DOI：10.1021/acs.orglett.1c01931

  日期：2021.8.6

  developed. The trans-vinylpalladium species, generated through intramolecular syn-carbopalladation of alkynes and subsequent cis-trans isomerization, were captured by hexamethyldisilane to form multisubstituted vinylsilanes. This reaction provides a useful strategy for the stereoselective synthesis of isoquinolinone-containing exocyclic tetrasubstituted vinylsilanes.

  已经开发了钯催化的炔烃的反式选择性碳甲硅烷基化反应。通过炔烃的分子内顺-碳钯化和随后的顺-反异构化产生的反式乙烯基钯物质被六甲基乙硅烷捕获以形成多取代的乙烯基硅烷。该反应为立体选择性合成含异喹啉酮的环外四取代乙烯基硅烷提供了一种有用的策略。
• Intermolecular C–H silylation through cascade carbopalladation and vinylic to aryl 1,4-palladium migration
  作者：Cang Cheng、Qiongqiong Zhu、Yanghui Zhang

  DOI：10.1039/d1cc03677g

  日期：——

  A palladium-catalyzed remote C–H silylation reaction has been developed through vinylic to aryl 1,4-palladium migration. By using alkyne-tethered aryl iodides as the starting materials and hexamethyldisilane as the silylating reagent, the reaction involves cascade intramolecular carbopalladation, 1,4-palladium migration, and silylation with hexamethyldisilane, and leads to the formation of exocyclic

  通过乙烯基到芳基 1,4-钯的迁移，开发了钯催化的远程 C-H 硅烷化反应。以炔系芳基碘化物为起始原料，六甲基乙硅烷为甲硅烷基化试剂，该反应涉及分子内碳钯化、1,4-钯迁移和六甲基乙硅烷的甲硅烷基化反应，生成含环外烯烃的5-甲硅烷基异喹啉作为最终产品。
• Metal-Free Oxidative <i>Ipso</i>-Carboacylation of Alkynes: Synthesis of 3-Acylspiro[4,5]trienones from <i>N</i>-Arylpropiolamides and Aldehydes
  作者：Xuan-Hui Ouyang、Ren-Jie Song、Yang Li、Bang Liu、Jin-Heng Li

  DOI：10.1021/jo5005982

  日期：2014.5.16

  A general and metal-free radical route to synthesis of 3-acylspiro[4,5]trienones is established that utilizes TBHP (tert-butyl hydrogenperwdde) as an oxidation and a reaction partner to trigger the oxidative ipso-carboacylation of N-arylpropiolamides with aldehydes. This method offers a new difunctionalization of alkynes through oxidative cross coupling of the aldehyde C(sp(2))-H bond with an ipso-aromatic carbon.