Review
Chemistry, Applied
Liguo Lu, Dayun Huang, Zefeng Wang, Xingyong Wang, Xiangmei Wu
Summary: Alkenes are valuable in organic synthesis, and they can be easily transformed into selenium or sulfur-containing compounds with a neighboring functional group via three-component reactions. This approach reduces the number of steps and waste generation while enabling the formation of complex molecules from simple starting materials. Recent developments in selenylation and thiolation reactions are summarized in this review, including various reactants such as electron-rich arenes, alcohols, water, acids, and other compounds. This review aims to provide insights for future research in this area.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Dingyi Wang, Binbin Yuan, Jiawei Xu, Lutz Ackermann
Summary: In this study, an electrochemical strategy was used to achieve the dual functionalization of unactivated alkenes through an intramolecular migration process. This strategy eliminated the need for sacrificial chemical oxidants and noble-metal catalysts, and the reactions were carried out under mild conditions. The electrochemistry enabled the migration of (hetero)aryl groups, leading to the formation of alkenyl/alkynyl-migration products. The reaction mechanism was established through experiments and computations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Sidi Cheng, Yu Luo, Ting Yu, Jing Li, Chunfang Gan, Shuang Luo, Qiang Zhu
Summary: An unactivated alkene was successfully subjected to 1,2-difunctionalization through a palladium-catalyzed four-component cascade reaction, leading to the convenient synthesis of acetamides with various substituents and pyrrolo-fused heterocycles.
Article
Chemistry, Multidisciplinary
Yunlong Wei, Hong Zhang, Xinxin Wu, Chen Zhu
Summary: The radical-mediated difunctionalization of alkenes introduces one alkenyl or alkynyl group to target compounds, but simultaneous installation of two unsaturated C-C bonds via alkene difunctionalization remains challenging due to the high instability of alkenyl and alkynyl radicals. This study reports the successful photocatalytic 1,2-alkynylalkenylation and 1,2-enynylalkenylation of alkenes, utilizing stabilized allenyl radicals for intermolecular addition, with a broad substrate scope and increased degree of unsaturation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhigang Ma, Xinxin Wu, Chen Zhu
Summary: Fluorine incorporation through fluoroalkyl radical addition and functional group migration is an ingenious and robust strategy for the synthesis of structurally diverse fluorinated compounds.
Review
Chemistry, Applied
Fei Zhou, Meng Li, Huanfeng Jiang, Wanqing Wu
Summary: This review highlights the recent advances in reaction development of electron-rich alkenes since 2000, including various types of reactions and methods for transforming them into valuable compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Organic
Jing-Hao Qin, Ning Nan, Jin-Heng Li
Summary: The electrochemical alkene difunctionalization reaction is an efficient and sustainable method for constructing vicinal difunctionalized structures in organic synthesis. It eliminates the need for additional redox catalysts, metal catalysts, or chemical oxidants and avoids the generation of chemical waste by solely using electrons as the redox agents. This review summarizes the recent advancements in electrochemical alkene difunctionalization, focusing on reaction features, scope, limitations, and mechanistic rationalizations of three categories of alkene difunctionalization methods: nucleophile-terminated, radical-terminated, and functionality migration-terminated reactions.
SYNTHESIS-STUTTGART
(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.
Review
Chemistry, Applied
Shintaro Kawamura, Pablo Barrio, Santos Fustero, Jorge Escorihuela, Jianlin Han, Vadim A. Soloshonok, Mikiko Sodeoka
Summary: The difunctionalizative trifluoromethylation of unsaturated C-C bonds is a highly useful and efficient method for synthesizing trifluoromethyl compounds. This review focuses on reactions that simultaneously form C-heteroatom and C-H bonds, providing useful CF3 group-containing building blocks. The comprehensive survey categorizes reactions into those that are synthetically mature and those with room for further development.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Sha Peng, Long-Yong Xie, Luo Yang
Summary: A convenient protocol for the preparation of SCF3-containing quinoxalin-2(1H)-one derivatives is developed using K2S2O8 mediated difunctionalization of alkenes with quinoxalinones and AgSCF3. Preliminary study indicates that a SCF3 radical triggered cascade reaction process may be involved in the current transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Sheng Xu, Herong Chen, Zhijun Zhou, Wangqing Kong
Summary: Catalytic alkene difunctionalization using decatungstate photo-HAT and nickel catalysis allows for the direct activation of aliphatic C-H bonds, enabling the installation of highly functionalized C(sp(3))-hybrid centers. This strategy demonstrates practicality in selective late-stage functionalization of natural products and concise synthesis of pharmaceutically relevant molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Subrata Patra, Ivan Mosiagin, Rahul Giri, Thomas Nauser, Dmitry Katayev
Summary: This paper introduces an electrochemically assisted method for generating nitryl radicals from ferric nitrate using inexpensive graphite and stainless-steel electrodes under mild reaction conditions. The reaction mechanism is supported by spectroscopic and experimental studies. The synthesis of diverse products is demonstrated through the development of highly efficient nitration protocols for various unsaturated hydrocarbons. These protocols have broad applications, are easily scalable for large quantities, and exhibit exceptional substrate generality and functional-group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jixin Wang, Donghao Luo, Ying Hu, Zhili Duan, Jianlin Yao, Konstantin Karaghiosoff, Jie Li
Summary: Simultaneous formation of carbon-carbon and carbon-heteroatom bonds through transition metal-catalyzed alkene difunctionalization is a powerful tool for synthetic organic chemistry. A new type of S- and P-stabilized bromoallenes for palladium-catalyzed modular allenation and borylation of alkenes has been developed, enabling the synthesis of multiply functionalized allenes in a highly selective manner. This method offers broad substrate scope and functional group compatibility, allowing for the facile installation of allenyl and boryl groups across alkenes.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Qi Tong, Ren-Feng Xiu, Jia-He Chen, Yun Zhang, Bao-Dong Cui, Nan-Wei Wan, Yong-Zheng Chen, Wen-Yong Han
Summary: A highly efficient rearrangement strategy for the synthesis of complex 2-amino-3-formyl chromones has been developed using palladium-catalyzed ring-opening, rearrangement, and cyclization processes. This method allows for the formation of multiple bonds and the reconstruction of the chromone moiety in a single step, making it atom- and step-economical. The synthetic application of this strategy has been demonstrated through various transformations and the synthesis of bioactive molecules and drugs.
Review
Chemistry, Multidisciplinary
Jie Huang, Zhi-Min Chen
Summary: The alkynylative difunctionalization of alkenes is an important synthetic method and has made significant progress in recent years. This review provides a comprehensive summary of this reaction, including alkynylation-initiated and alkynylation-terminated difunctionalizations of alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
