tert-butyl (E)-(2-styrylphenyl)carbamate | 909297-32-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: tert-butyl (E)-(2-styrylphenyl)carbamate
• 英文别名: tert-Butyl (2-styrylphenyl)carbamate；tert-butyl N-[2-[(E)-2-phenylethenyl]phenyl]carbamate
• CAS: 909297-32-1
• 化学式: C₁₉H₂₁NO₂
• 分子量: 295.381
• InChiKey: RQMLVXXQKRBKFA-BUHFOSPRSA-N

物化性质

• 熔点：
  119-121 °C
• 沸点：
  386.9±22.0 °C(Predicted)
• 密度：
  1.128±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl (E)-(2-styrylphenyl)carbamate 在 tert-butylammonium hexafluorophosphate(V) 作用下， 以 乙腈 为溶剂， 以42 %的产率得到tert-butyl 2-phenyl-1H-indole-1-carboxylate
  参考文献：
  名称：

  1,2-二芳基烯烃衍生物杂环的无金属和无氧化剂电合成

  摘要：

  已经发现在无金属和无氧化剂的条件下通过电合成从 1,2-二芳基烯烃衍生物合成杂环。2-烯基苯甲酸的阴极还原或 2-烯基苯甲酰胺、2-烯基苯酚和 2-烯基苯胺的阳极氧化导致反应性自由基中间体的形成，这些中间体提供相应的苯酞、异色满-1-酮、异吲哚啉-1-酮、苯并呋喃和吲哚以良好的官能团耐受性满足产量。有趣的是，在不同的反应溶剂中发现了不同的化学选择性。进行了几项机理研究，包括循环伏安法研究和控制实验，以阐明反应机理。

  DOI：

  10.1002/adsc.202200847
• 作为产物：
  描述：

  2-溴苯胺 在 palladium diacetate 、 三乙胺 、 对甲苯磺酰氯 、 三(邻甲基苯基)磷 作用下， 以 邻二氯苯 为溶剂， 反应 2.0h， 生成 tert-butyl (E)-(2-styrylphenyl)carbamate
  参考文献：
  名称：

  DMSO / SOCl2介导的C（sp2）–H胺化：3-未取代的吲哚和3-甲基硫代吲哚衍生物的可转换合成

  摘要：

  发现2-烯基苯胺与SOCl 2在DMSO中的反应选择性地提供3-未取代的吲哚和3-甲基硫代吲哚。发现这种可转换的方法是温度依赖性的：在室温下，该反应通过分子内环化和消除得到3-未取代的吲哚；在较高温度下，反应通过进一步的亲电甲基硫醇化反应生成3-甲基硫吲哚。

  DOI：

  10.1039/d0cc07453e

文献信息

• Regioselective Synthesis of 2-Vinylanilines Using <i>O</i>-aroyloxycarba-mates by Sequential Decarboxylation/Amination/Heck Reaction
  作者：Peihe Li、Nuannuan Ma、Jikun Li、Zheng Wang、Qipu Dai、Changwen Hu

  DOI：10.1021/acs.joc.7b01020

  日期：2017.8.4

  ortho-substituted substrates, but also provides site-special to create new C(sp2)-N and C(sp2)-C(sp2) bonds. Mechanistic experiments suggest the cleavage of C(sp2)-COOH gives priority to C(sp2)-X bond in this reaction.

  描述了利用芳基羧酸作为稳定，廉价和广泛可获得的芳基化试剂的2-乙烯基苯胺的新的顺序方法。采用Pd-POVs催化剂体系，该方案不仅克服了脱羧偶联到邻位取代底物上的限制障碍，而且还提供了特殊的位置来生成新的C（sp 2）-N和C（sp 2）-C （sp 2）债券。机理实验表明，在该反应中，C（sp 2）-COOH的裂解优先于C（sp 2）-X键。
• Rhodium(III)-Catalyzed <i>Ortho</i>-Alkenylation of Anilines Directed by a Removable Boc-Protecting Group
  作者：Tomohiro Morita、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/acs.orglett.7b00569

  日期：2017.4.7

  The rhodium(III)-catalyzed ortho-alkenylation of N-Boc-anilines with alkenes such as acrylate ester and styrene proceeds smoothly through C–H bond cleavage. Obtained o-alkenylanilines can be readily transformed to nitrogen-containing fused heteroaromatic compounds including indoles and quinolines.

  铑（III）催化的N -Boc苯胺与烯烃（如丙烯酸酯和苯乙烯）的邻烯基化通过CH键断裂而顺利进行。获得的邻烯基苯胺可以容易地转化为含氮的稠合杂芳族化合物，包括吲哚和喹啉。
• Metal-Free C–H Amination for Indole Synthesis
  作者：Young Ho Jang、So Won Youn

  DOI：10.1021/ol5015398

  日期：2014.7.18

  An effective metal-free C-H amination of N-Ts-2-alkenylanilines by using DDQ as an oxidant has been developed to afford a diverse range of substituted indoles. This protocol is operationally simple and robust, obviates the need of expensive transition-metal catalysts, and offers a broad substrate scope. A mechanism involving a radical cation generated by SET and a migratorial process via a phenonium ion intermediate is proposed.
• Carbolithiation of <i>o</i>-Amino-(<i>E</i>)-Stilbenes:  Diastereoselective Electrophile Substitution with Applications to Quinoline Synthesis
  作者：Anne-Marie L. Hogan、Donal F. O'Shea

  DOI：10.1021/jo7017679

  日期：2007.12.1

  [GRAPHICS]A regioselective carbolithiation of o-amino-(E)-stilbenes has been achieved with a series of alkyllithiums when THF is employed as the reaction solvent. The use of other solvents, such as diethyl ether or hydrocarbons, leads to a pronounced loss in regioselectivity. Moreover, high levels of diastereoselectivity have been obtained following reaction of the lithiated intermediate in THF with different electrophiles such as MeOD, CO2, and Bu3SnCl. It was shown that diastereoselectivity was influenced by the ortho-amino substituent and the alkyllithium utilized for carbolithiation with N-Boc substituent and t-BuLi proving optimal. In the case of carbolithiated intermediate 3a, obtained from the reaction of N-Boc substituted stilbene with t-BuLi, H-1 and C-13 NMR analysis revealed predominantly one diastereoisomer which was stable at room temperature. Application of the carbolithiation/electrophile reaction methodology to the synthesis of six-membered quinoline ring systems is demonstrated with substituted 3,4-dihydroquinolin-2-ones, 1,2,3,4-tetrahydroquinolines, 1,4-dihydroquinolines, and quinolines all prepared by a common cascade route.
• Regioselective Carbolithiation of <i>o</i>-Amino-(<i>E</i>)-Stilbenes:  Cascade Route to the Quinoline Scaffold
  作者：Anne-Marie L. Hogan、Donal F. O'Shea

  DOI：10.1021/ol061348n

  日期：2006.8.1

  The regioselective carbolithiation of substituted ortho-amino-(E)-stilbenes can be exploited to initiate cascade reaction sequences that can be utilized as new routes to substituted 3,4-dihydro-1H-quinolin-2-ones,1,2,3,4-tetrahydroquinolines, 1,4-dihydroquinolines, and quinolines.