Article
Chemistry, Organic
Chao Liu, Xiangwen Tan, Jinhui Zhang, Jiahao Wu, Wanqing Wu, Huanfeng Jiang
Summary: This article describes a palladium (II)-catalyzed Nu/Nu'-type 1,1-oxamidation and 1,1-diamination reaction of unactivated alkenyl carbonyl compounds followed by amination. The reaction features a lack of a directing group, good functional group tolerance, and easily operational catalytic reaction conditions. Mechanistic investigations suggest a unique route involving two consecutive nucleopalladations for this 1,1-difunctionalization.
Article
Chemistry, Organic
Stanislav A. Paveliev, Oleg O. Segida, Andrey Dvoretskiy, Mark M. Dzyunov, Uliana Fedorova, Alexander O. Terent'ev
Summary: A novel electrochemical process was developed for the difunctionalization of vinyl arenes with N-hydroxyphthalimide, resulting in vicinal dioxyphthalimides. The reaction involves the anodic generation of stabilized phthalimide-N-oxyl radical, which adds to the carbon-carbon double bond of vinyl arenes and recombines with the subsequently formed benzylic radical to afford a wide range of dioxyphthalimides with yields up to 81%.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Fangming Chen, Lvqi Jiang, Chunyang Hu, Jie Liu, Wenbin Yi
Summary: This study reports an unprecedented usage of CF3SO2Na as a radical trifluoromethylthiolation reagent. A photocatalyzed ditrifluoromethylthiolation reaction of alkenes with CF3SO2Na in the presence of PPh(3 )and catalytic copper has been developed. Mechanistic studies reveal two different photocatalytic quenching mechanisms.
SCIENCE CHINA-CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Xiaoming Ma, Qiang Zhang, Wei Zhang
Summary: Radical transformations are powerful tools in organic synthesis for constructing molecular scaffolds and introducing functional groups. Radical difunctionalization reactions allow radicals to be relocated through resonance, hydrogen transfer, and ring opening, enabling the synthesis of 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalization products. These reactions offer synthetic efficiency, operational simplicity, and product diversity, making them advantageous for remote difunctionalization.
Article
Chemistry, Multidisciplinary
Qing-Yun Fang, Jie Han, Mingzhe Qin, Weipeng Li, Chengjian Zhu, Jin Xie
Summary: Reported here is a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides, and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au-3(tppm)(2)](OTf)(3). This reaction enables facile 1,2-aminoalkylation and 1,2-alkylarylation and exhibits a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96% yield). It also provides a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C-Br bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Liang Zeng, Jing-Hao Qin, Gui-Fen Lv, Ming Hu, Qing Sun, Xuan-Hui Ouyang, De-Liang He, Jin-Heng Li
Summary: Here, the authors report a new electrophotocatalytic intermolecular reductive 1,2-diarylation of alkenes using aryl halides and cyanoaromatics. The reaction demonstrates a broad substrate scope, excellent functional group compatibility, and excellent selectivity. Mechanistic investigations suggest a radical process initiated by the reductive generation of aryl radicals from aryl halides and terminated by radical-radical coupling with cyanoaromatic radical anions.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhu Cao, Huihui Zhang, Xinxin Wu, Yahong Li, Chen Zhu
Summary: The research achieved the heteroarylation of unactivated aliphatic C-H bonds through radical-mediated heteroaryl migration, leading to a variety of heteroaryl-substituted aliphatic ketones. The method is applicable to O-/S-/N-containing heteroaryls and features mild C-C bond cleavage and good selectivity for tertiary C-H bonds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Mingze Sun, Jingjing Chen, Zhenhua Ding
Summary: A new method for the regioselective cyclization of α-aminated ketones to form oxazolidines and dihydroxazines under transition metal-free conditions has been developed. The reaction proceeds at room temperature without the need for hypervalent iodine reagents and gives good to excellent yields of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nina Diesendorf, Pia Wenisch, Janina Oppl, Markus R. Heinrich
Summary: This article describes the functionalization of arenes and alkenes through additive-free radical reactions using highly photosensitive, fluorescein-derived diazonium salts. The unique properties of diazonium salts enable Meerwein-type carbohydroxylation of non-activated alkenes, which can be rationalized by a reaction mechanism involving forth and back electron transfer from and to the xanthene subunit of the fluorescein moiety.
Article
Chemistry, Organic
Meiqi Zhang, Weizhe Zhao, Jiamin Ma, Jiaoxiong Li, Qiansen Meng, Chengshuo Shen, Xianghua Zeng
Summary: A copper-powder-catalyzed syn-selective chlorosulfonylation reaction has been developed, providing access to a range of (Z)-beta-chlorovinylsulfones in good yields. This ligand-free method features excellent stereoselectivity and high atom economy.
Article
Chemistry, Multidisciplinary
Nils Lennart Frye, Constantin G. Daniliuc, Armido Studer
Summary: In this study, a transition-metal-free radical 1,2-difunctionalization method was developed to access beta-alkynyl-fluorosulfonylalkanes. The obtained compounds could be diversified into sulfonates and sulfonamides using SuFEx click chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Min Liu, Bifu Liu, Qian Wang, Kejun Feng, Yuanhua Li, Lixin Liu, Jiaen Tong
Summary: A novel and efficient metal-free cascade oxidative radical addition of styrenes has been developed for the construction of 1,3-dichloro-1,5-diarylpentan-5-ones. This protocol offers a practical one-pot procedure that provides highly functionalized 1,3-dichloro-1,5-diarylpentan-5-ones in moderate-to-good yields with a broad substrate scope under mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Chi Gao, Yang Liu, Hong-Ye Zhu, Mang Wang
Summary: A simple and environmentally friendly method for olefinic thiocyanotrifluoromethylation has been developed, which selectively occurs on water at ambient condition. The method is compatible with different substituted alkenes and also suitable for the selenocyanotrifluoromethylation of alkenes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis is achieved in asymmetric photocatalysis using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer. Different inorganic bases enable the formation of valuable products from the three-component radical tandem transformations. The distinct pKa environment plays a key role in the success of this process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis was achieved using asymmetric photocatalysis. By using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases were used to enable the formation of two sets of valuable products from a three-component radical tandem transformation. The key to success was the distinct pK(a) environment, which determined the fate of the radicals formed on the quinoxalin-2(1H)-one rings.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
