(E)-1,2-diphenyldiazene-d10 | 192059-57-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: (E)-1,2-diphenyldiazene-d10
• 英文别名: (E)-1,2-diphenyldiazene-d₁₀；dipentadeuteroazobenzene；azobenzene-d10；trans-bis-pentadeuteriophenyl-diazene
• CAS: 192059-57-7
• 化学式: C₁₂H₁₀N₂
• 分子量: 192.145
• InChiKey: DMLAVOWQYNRWNQ-NDVYENKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.72
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-1,2-diphenyldiazene-d10 以 二甲基亚砜 为溶剂， 生成 (Z)-1,2-bis(phenyl-d5)diazene
  参考文献：
  名称：

  Deuteration as a General Strategy to Enhance Azobenzene‐Based Photopharmacology

  摘要：

  Chemical photoswitches have become a widely used approach for the remote control of biological functions with spatiotemporal precision. Several molecular scaffolds have been implemented to improve photoswitch characteristics, ranging from the nature of the photoswitch itself (e.g. azobenzenes, dithienylethenes, hemithioindigo) to fine‐tuning of aromatic units and substituents. Herein, we present deuterated azobenzene photoswitches as a general means of enhancing the performance of photopharmacological molecules. Deuteration can improve azobenzene performance in terms of light sensitivity (higher molar extinction coefficient), photoswitch efficiency (higher photoisomerization quantum yield), and photoswitch kinetics (faster macroscopic rate of photoisomerization) with minimal alteration to the underlying structure of the photopharmacological ligand. We report synthesized deuterated azobenzene‐based ligands for the optimized optical control of ion channel and G protein‐coupled receptor (GPCR) function in live cells, setting the stage for the straightforward, widespread adoption of this approach.

  DOI：

  10.1002/anie.202408300
• 作为产物：
  描述：

  苯胺-2,3,4,5,6-d5 在 吡啶 、 氧气 、 copper(I) bromide 作用下， 以 甲苯 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 以52%的产率得到(E)-1,2-diphenyldiazene-d10
  参考文献：
  名称：

  I通过可分离的环状R（I）配合物催化偶氮苯和醛的[4 +1]环化

  摘要：

  首次开发了用醛对偶氮苯进行再催化的[4 +1]环合反应，以通过可分离和表征的环状Re I-络合物提供2 H-吲唑。在重新催化的C–H活化反应中，乙酸促进作用首次显示出来。值得注意的是，机理研究表明，醛的插入步骤不可逆，这与以前的Rh和Co体系的形成强烈反差。

  DOI：

  10.1021/acs.orglett.5b00938

文献信息

• Rhodium(III)-Catalyzed Synthesis of Cinnolinium Salts from Azobenzenes and Diazo Compounds
  作者：Xiaohong Chen、Guangfan Zheng、Guoyong Song、Xingwei Li

  DOI：10.1002/adsc.201800326

  日期：2018.8.6

  A Rh(III)‐catalyzed C−H activation of azobenzenes in the coupling with diazo compounds has been realized, providing a straightforward strategy to access functionalized cinnolinium triflates in high yields. This protocol features silver free mild reaction conditions and compatibility with diverse functional groups. The coupling proceeds via initial Rh(III)‐catalyzed C−H alkylation, followed by zinc

  与重氮化合物偶合后，已实现了Rh（III）催化的偶氮苯的CH活化，从而提供了一种直接的方法来以高收率获得官能化的三氟甲烷磺酸。该协议的特点是无银温和的反应条件以及与各种官能团的相容性。偶联过程通过最初的Rh（III）催化的CH烷基化反应进行，随后是三氟甲磺酸锌介导的环化反应，其中三氟甲磺酸锌既充当路易斯酸又是三氟甲磺酸来源。
• Rhenium-catalyzed C–H aminocarbonylation of azobenzenes with isocyanates
  作者：Xiaoyu Geng、Congyang Wang

  DOI：10.1039/c5ob01121c

  日期：——

  The first C–H aminocarbonylation of azobenzenes with isocyanates is achieved by using rhenium-catalysis, which provides an atom-economical access to o-azobenzamides.

  使用铼催化剂实现了偶氮苯与异氰酸酯的第一次C-H氨基羰化反应，从而提供了一种原子经济的方法合成o-偶氮苯酰胺。
• <i>ortho</i>-Heteroarylation of Azobenzenes by Rh-Catalyzed Cross-Dehydrogenative Coupling: An Approach to Conjugated Biaryls
  作者：Hong Deng、Hongji Li、Lei Wang

  DOI：10.1021/acs.orglett.6b01277

  日期：2016.7.1

  A direct cross-dehydrogenative coupling strategy for ortho-C–H activation and functionalization of azobenzenes with heteroarenes in the presence of a Rh catalyst was developed. Excellent regioselectivity was achieved by azo-coordinated Rh to realize oxidative C–H/C–H cross-coupling, providing a series of π-conjugated biaryls in good yields.

  在Rh催化剂的存在下，开发了一种直接的交叉脱氢偶联策略，用于邻-C–H活化和偶氮苯与杂芳烃的官能化。通过偶氮配位的Rh实现氧化的C–H / C–H交叉偶联，具有出色的区域选择性，从而以高收率提供了一系列π共轭联芳基。
• Cp*Co(<scp>iii</scp>)-catalyzed ortho-amidation of azobenzenes with dioxazolones
  作者：Gongutri Borah、Preetismita Borah、Pitambar Patel

  DOI：10.1039/c7ob00540g

  日期：——

  Cp*Co(III)-catalyzed C–H amidation of azobenzene with dioxazolones has been developed. The amidation reaction does not require external oxidants and gives carbon dioxide as the only by-product. Both symmetrical and unsymmetrical azobenzenes were found to undergo amidation smoothly with broad functional group tolerance.

  已经开发了Cp * Co（III）催化的偶氮苯与二恶唑酮的CHH酰胺化反应。酰胺化反应不需要外部氧化剂，并且产生二氧化碳作为唯一的副产物。发现对称和不对称的偶氮苯均能平稳地进行酰胺化反应，并具有宽泛的官能团耐受性。
• Site-Selective C-H Amidation of Azobenzenes with Dioxazolones under Rhodium Catalysis
  作者：Neeraj Kumar Mishra、Yongguk Oh、Mijin Jeon、Sangil Han、Satyasheel Sharma、Sang Hoon Han、Sung Hee Um、In Su Kim

  DOI：10.1002/ejoc.201601096

  日期：2016.10

  The rhodium(III)-catalyzed amidation reaction of azobenzenes with dioxazolones is described. This strategy allows the facile and efficient construction of highly substituted ortho-amidated azobenzenes via direct C-H cleavage approach. A range of substrate scope, excellent levels of chemoselectivity as well as high functional group tolerance were observed. In addition, this protocol was used to generate

  描述了铑 (III) 催化的偶氮苯与二恶唑酮的酰胺化反应。该策略允许通过直接 CH 裂解方法轻松有效地构建高度取代的邻位酰胺化偶氮苯。观察到一系列底物范围、优异的化学选择性以及高官能团耐受性。此外，该协议还用于生成一系列邻酰胺化酮。酰胺化偶氮苯的进一步合成转化为苯并咪唑和苯并三唑衍生物的构建提供了便利。