Minimization of Back‐Electron Transfer Enables the Elusive sp
<sup>3</sup>
C−H Functionalization of Secondary Anilines
作者:Huaibo Zhao、Daniele Leonori
DOI:10.1002/anie.202100051
日期:2021.3.29
Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N‐Dialkyl‐derivatives enable radicalgenerationα to the N‐atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back‐electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence
Arylamines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to arylaminesynthesis using dehydrative amination of phenols with amines and styrene under continuous‐flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding arylamines, with small amounts
Synthesis of Spiro-dihydroquinoline and Octahydrophenanthrene Derivatives via Palladium-Catalyzed Intramolecular Oxidative Arylation
作者:Zhong-Lin Zang、Shuklachary Karnakanti、Sheng Zhao、Ping Hu、Zhen Wang、Pan-Lin Shao、Yun He
DOI:10.1021/acs.orglett.7b00228
日期:2017.3.17
A method for intramolecular sp2 C–H oxidative arylation of unactivated cyclic olefins has been developed to access spiro-dihydroquinoline and octahydrophenanthrene derivatives in a straightforward and efficient manner. Bearing picolinamide as a directing group, the alkenyl anilines cyclized to afford spiro-dihydroquinolines in moderate to excellent yields via direct oxidative arylation, while the alkenyl
Ligand‐Controlled, Tunable Copper‐Catalyzed Radical Divergent Trifluoromethylation of Unactivated Cycloalkenes
作者:Qi Wang、Zhong‐Lin Zang、Mi Jie、Li‐Hua Luo、Dan Yang、Cheng‐He Zhou、Gui‐Xin Cai
DOI:10.1002/adsc.202101016
日期:2021.12.7
The Cu-catalyzed high-chemoselective trifluoromethylation reactions of unactivated cycloalkenes via the modulation of appropriate ligands have been explored. The Cu(I)/appropriate ligands-catalytic systems overcome the key challenge in differentiating two pathways involving radical intermediates and provide a ligand-controlled approach for site-specific spiro-aryltrifluoromethylation and chlorotrifluoromethylation
已经探索了通过调节合适的配体对未活化的环烯烃进行 Cu 催化的高化学选择性三氟甲基化反应。Cu(I)/适当的配体催化系统克服了区分涉及自由基中间体的两条途径的关键挑战,并为位点特异性螺芳基三氟甲基化和氯三氟甲基化提供了一种配体控制的方法,以提供三氟甲基化的螺四氢喹啉化合物和邻位含氯的化合物三氟甲基环烷烃。此外,与报道的氯源相比,1,2-二氯乙烷被用作三氟氯甲基化的更绿色、更经济的原料。
Intramolecular nitration–aminocarbonylation of unactivated olefins: metal-free synthesis of γ-lactams
作者:Dong Chen、Meishan Ji、Chen Zhu
DOI:10.1039/c9cc03736e
日期:——
Disclosed herein is a novel, metal-free synthesis of γ-lactams through the radical-mediated nitration–aminocarbonylation of unactivated olefins. The reaction is initiated by a nitro radical generated from the homolysis of tert-butyl nitrite. The intramolecular cyanamide serves as the aminocarbonylating reagent. This protocol offers an environment-benign method to produce the synthetically valuable