Article
Chemistry, Multidisciplinary
Andrew G. Dalling, Georg Spath, Alois Furstner
Summary: This article reports the first total synthesis of a tetracyclic marine pyridinium alkaloid, which was achieved using recent advances in chemoselectivity management. The synthesis involved the formation of critical C-C bond using nickel/iridium photoredox dual catalysis, successful ring closing alkyne metathesis (RCAM) despite the presence of a Lewis acidic alkylidyne catalyst, and a unique iridium catalyzed hydrosilylation reaction. The synthesis also demonstrated site- and chemoselective intramolecular N-alkylation for closing the second strained macrocycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Anastasia L. Gant Kanegusuku, Jennifer L. Roizen
Summary: Photomediated Giese reactions have become a forefront in radical chemistry, utilizing organometallic photocatalysts to generate carbon-centered radicals. Chemists have developed numerous strategies to access crucial carbon-centered radical intermediates for radical conjugate addition processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Tao Xiong, Qian Zhang
Summary: Recent decades have seen unprecedented growth in the development of new synthetic methods involving radical intermediates to control the absolute configuration of newly formed stereocenters.The catalytic asymmetric direct construction of stereocenters through addition of radicals to internal alkenes is of special interest due to its potential to simultaneously build more than two consecutive stereogenic centers. Methodologies like chiral Lewis acid catalysis, organocatalysis, and transition metal catalysis have been effectively utilized in this challenging domain, highlighting significant progress in the rapid and convenient construction of enantioenriched stereocenters.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Jing Cao, Antonia Seitz, Jose A. Forni, Anastasios Polyzos, David W. Lupton
Summary: This article reports on a reaction design that avoids the facile oxidation of phosphine organocatalyst and combines traditional nucleophilic phosphine organocatalysis with photoredox catalysis to enable Giese coupling with ynoates. The approach exhibits good generality, and its mechanism is supported by cyclic voltametric, Stern-Volmer quenching, and interception studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Weihui Zhuang, Yuan-Zheng Cheng, Xu-Lun Huang, Qiufeng Huang, Xiao Zhang
Summary: A photocatalytic protocol for the divergent dearomative functionalization of indole derivatives has been reported. By modifying the reaction conditions, either dimerization or reduction can selectively occur under visible light irradiation, leading to the formation of cyclobutane-fused polycycles and 2-substituted indolines in good yields with exclusive selectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Albert Granados, Roshan K. Dhungana, Mohammed Sharique, Jadab Majhi, Gary A. Molander
Summary: This article presents a simple and practical method for the difunctionalization of styrenes, producing fluorinated benzyl bromides through a photoinduced atom transfer radical addition process. The method is mild, cost-effective, requires low photocatalyst loading (1000 ppm), and is highly compatible with various functional groups on styrene. The versatility of the fluorinated benzyl bromides is demonstrated through their derivatization to valuable compounds.
Article
Chemistry, Organic
Qiao-Fei Bao, Ming Li, Yu Xia, Yu-Zhao Wang, Zhao-Zhao Zhou, Yong-Min Liang
Summary: The photocatalytic decarboxylative radical addition bifunctionalization cascade presented in this study relies on single-electron transfer to complete the catalytic cycle. The reaction offers advantages such as the use of commercially available materials, wide functional group compatibility, and mild conditions. Importantly, some amino acids and bioactive carboxylic acids can provide corresponding products in moderate to good yields, highlighting their potential value in drug development.
Article
Chemistry, Multidisciplinary
Helian Li, Yongxin Zhang, Xiaoxiao Yang, Zhenxi Deng, Zhimin Zhu, Pan Zhou, Xinke Ouyang, Yuting Yuan, Xi Chen, Lingyue Yang, Meng Liu, Chao Shu
Summary: This study reports a photoredox-catalyzed multifluoromethyl radical addition/SO2 incorporation/polar cyclization cascade approach for the synthesis of multifluoromethylated gamma-sultines. The reactions proceed by single electron transfer induced multifluoromethyl radical addition to an alkene followed by SO2 incorporation and single-electron reduction for polar 5-exo-tet cyclization. The use of easily oxidizable multifluoroalkanesulfinates as bifunctional reagents is key to the success of this protocol. The reactions exhibit excellent functional-group tolerance and deliver gamma-sultines in moderate to excellent yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiangpei Chai, Xinheng Hu, Xiaowei Zhao, Yanli Yin, Shanshan Cao, Zhiyong Jiang
Summary: This research reports a radical-based manifold that achieves highly enantioselective transformations of N-arylglycines. The dual catalytic system involving a chiral phosphoric acid and a photoredox sensitizer offers a new approach for the synthesis of valuable organic compounds with satisfactory results and high enantiocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Felix Schaefers, Subhabrata Dutta, Roman Kleinmans, Christian Mueck-Lichtenfeld, Frank Glorius
Summary: A general strategy is reported in this paper to access a variety of valuable homoallylic alcohols with opposite chemo- and diastereoselectivity by switching to photocatalytic activation in combination with a closed transition state.
Article
Chemistry, Applied
Lili Zhang, Yuhang Li, Zhenyu Guo, Yantao Li, Nian Li, Weipeng Li, Chengjian Zhu, Jin Xie
Summary: We describe the 1,6-addition reaction of acyl radicals to electron-deficient 1,3-dienes using visible-light photoredox catalysis. Mild conditions enable the deoxygenative allylation of carboxylic acids, producing valuable 1,6-dicarbonyl compounds with moderate to good yields (up to 96%). This protocol shows high regio- and stereo-selectivity, as well as good compatibility with various functional groups.
CHINESE JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yu-Chao Wang, Zhao-Xin Xiao, Miao Wang, Shao-Qian Yang, Jin-Biao Liu, Zhi-Tao He
Summary: This study presents modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis, which has been considered unfeasible. The results show that the 1,5-conjugate addition products can be conveniently transformed into various privileged enantioenriched motifs, indicating the potential applications of this method in synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Subhasis Paul, Dario Filippini, Mattia Silvi
Summary: The intermolecular addition of alkyl radicals to alkenes is a fundamental process in organic chemistry but is limited by electron deficiency of the alkene component. In this study, a polarity transduction strategy is introduced to overcome this electronic limitation. Vinyl sulfonium ions react with carbon-centered radicals to provide products that are otherwise inaccessible. The generality of this strategy is demonstrated through the derivatization of unmodified complex bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pauline Bianchi, Jason D. Williams, C. Oliver Kappe
Summary: Metal oxides are abundant and non-toxic photocatalysts for organic transformations, but their use in larger scale processes is complicated by incompatibilities with continuous flow processing. However, by utilizing a sustainable solvent system and low loading of Bi2O3, an efficient atom transfer radical addition protocol has been developed with high throughput and recyclability.
Article
Chemistry, Organic
Noelia Salaverri, Benedetta Carli, Sergio Diaz-Tendero, Leyre Marzo, Jose Aleman
Summary: In this study, the enantioselective addition of remote alkyl radicals to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid was reported. High yields and enantioselectivities up to 99% were achieved within 1 hour. Mechanistic investigations supported the formation of remote alkyl radicals through a proton-coupled electron transfer (PCET) process, and theoretical studies explained the observed stereochemistry in the addition step.
Article
Chemistry, Multidisciplinary
Shupeng Zhou, Hao Chen, Yijie Luo, Wenhao Zhang, Ang Li
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2015)
Article
Chemistry, Multidisciplinary
Jian Li, Wenhao Zhang, Fei Zhang, Yu Chen, Ang Li
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
News Item
Chemistry, Multidisciplinary
Wenhao Zhang, Ang Li
Article
Chemistry, Multidisciplinary
Wenhao Zhang, Ming Ding, Jian Li, Zhicong Guo, Ming Lu, Yu Chen, Lianchao Liu, Yun-Heng Shen, Ang Li
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Multidisciplinary
Yu Sun, Ruofan Li, Wenhao Zhang, Ang Li
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2013)
Article
Chemistry, Multidisciplinary
Jun Deng, Shupeng Zhou, Wenhao Zhang, Jian Li, Ruofan Li, Ang Li
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2014)
Article
Chemistry, Multidisciplinary
Yu Chen, Wenhao Zhang, Lu Ren, Jian Li, Ang Li
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
