Article
Chemistry, Physical
Linda Quach, Subhabrata Dutta, Philipp M. Pfluger, Frederik Sandfort, Peter Bellotti, Frank Glorius
Summary: This study presents a visible-light-promoted strategy for the selective anti-Markovnikov hydrooxygenation of unactivated alkenes. A carefully designed reagent releases a highly reactive and strongly underdeveloped alkoxycarbonyloxyl radical upon reduction, which selectively adds into the alkenes. This methodology expands the toolbox for regioselective hydrofunctionalization and could serve as a complementary strategy to the established hydroboration/oxidation protocol.
Article
Chemistry, Multidisciplinary
Yasuyuki Ura
Summary: This paper describes the challenging realization of anti-Markovnikov selectivity in Pd-catalyzed reactions, with key factors including the steric bulkiness of oxygen nucleophiles and electron-deficient cyclic alkenes as additives.
Article
Chemistry, Multidisciplinary
Yijie He, Chaoyu Du, Jian Han, Jie Han, Chengjian Zhu, Jin Xie
Summary: In this report, a practical protocol for the synthesis of arylethylamine functionality common in pharmaceutical chemicals has been developed. The protocol proceeds by Mn-catalyzed anti-Markovnikov hydroarylation of electron-rich enamides under mild conditions without the use of ligands. Both terminal and internal enamides can be regioselectively hydroarylated with various aryl boronic acids in 15 min. The reaction also allows for the hydroalkenylation of enamides with alkenyl boronic acids in air atmosphere, providing an elegant route to synthetically useful beta-alkenylated amines in satisfactory yields.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Bai-Yu Qian, Wei Zhang, Jin-Hong Lin, Weiguo Cao, Ji-Chang Xiao
Summary: In this paper, a convenient anti-Markovnikov iodofluorination of alkenes was described using Selectfluor/(Bu4NI)-Bu-n as the reagent. The reaction showed a broad substrate scope, good functional group tolerance, and the ability to construct various C-F bonds.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Engineering, Environmental
Jinfang Kou, Jian Fang, Jianfeng Li, Huacheng Zhao, Mengmeng Gao, Gong Zeng, Wei David Wang, Fengwei Zhang, Jiantai Ma, Zhengping Dong
Summary: In this study, a series of covalent organic frameworks (COFs)-anchored single-site Pt catalysts were prepared for efficient alkene hydrosilylation. The catalyst showed excellent activity and selectivity towards alkenes under solvent-free conditions, and maintained high catalytic stability during recycling experiments.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Organic
Mingdong Jiao, Xianjie Fang
Summary: A novel synthesis of homoallylic nitriles via cobalt-catalyzed hydrocyanation of methylenecyclopropanes is described. The protocol demonstrates excellent selectivity, mild reaction conditions, good functional group compatibility, gram-scale reaction, and product transformations. The extraordinary selectivity is probably attributed to the stronger aptitude of the alkyl-cobalt cyanide intermediate for reductive elimination rather than beta-hydride elimination.
Article
Biochemistry & Molecular Biology
Liang Nie, Xiangjun Peng, Haiping He, Jian Hu, Zhiyang Yao, Linyi Zhou, Ming Yang, Fan Li, Qing Huang, Liangxian Liu
Summary: This study investigates the synergistic role of catalytic systems driven by graphene oxide and visible light, enabling anti-Markovnikov addition to terminal alkenes and subsequent difunctionalization with N-methylquinoxalones. The photoinduced cascade radical difunctionalization of olefins provides a concise and applicable protocol for constructing alkoxyl-substituted N-methylquinoxalones.
Article
Chemistry, Organic
Wencheng Han, Wen-Deng Liu, Junqi Su, Jiannan Zhao
Summary: In this study, iminyl radicals were generated through photocatalytic deoxygenation of oximes with trivalent phosphine. The hydroimination reaction proceeded via beta-scission of a phosphoranyl radical, followed by 5-exo-trig cyclization of the resulting iminyl radical. This protocol transforms oximes, including alkyl oximes, into a variety of pyrrolines in moderate to good yields. A radical clock experiment confirmed the formation of a cyclic radical and supported our reaction design.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sheng-Qiang Lai, Bang-Yi Wei, Jia-Wei Wang, Wei Yu, Bing Han
Summary: A tunable photocatalytic method using ketoxime carbonates as reagents has been developed for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes. The reaction is initiated by N-O bond homolysis of ketoxime carbonates under visible-light photocatalysis, followed by generation of alkoxylcarbonyloxyl and iminyl radicals leading to carbon radical addition to alkenes. The carbon radical can either abstract a hydrogen atom to form hydrooxygenation product or be trapped by iminyl radical to yield aminooxygenation product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Yasuyuki Ura
Summary: The review summarizes recent progress in Pd-catalyzed anti-Markovnikov oxidation of terminal alkenes to provide terminally oxyfunctionalized organic compounds. Key additives like BQs are highlighted for enhancing the nucleophilic attack of oxygen nucleophiles on terminal alkenes. Various factors affecting the selectivity of the reaction, including steric hindrance of nucleophiles and substrate addition rate, are also discussed.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Fei Cheng, Li-Li Wang, Yuan-Hu Mao, Yong-Xi Dong, Bin Liu, Gao-Feng Zhu, Yuan-Yong Yang, Bing Guo, Lei Tang, Ji-Quan Zhang
Summary: An efficient aerobic iron-catalyzed annulation method for unsaturated carboxylic acids with disulfides has been developed, providing practical access to a wide range of substituted gamma-lactone derivatives. The disclosed method is simple, highly atom-economic, environmentally friendly, and tolerates a broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shihao Li, Chenglong Zheng, Sheng Wang, Xiao-Xuan Li, Qi Zhang, Shilu Fan, Yi-Si Feng
Summary: A novel three-component alpha-acylated difunctionalization strategy has been developed using a direct hydrogen atom transfer process of photoinduced acyl azolium salts. Various olefins can be directly converted into ketone derivatives, including 1,4-dione, beta-silyl ketone, 1,5-dione, etc., with simple irradiation without the need for a catalyst.
Article
Multidisciplinary Sciences
Jieping Chen, Jiale Ying, Zhan Lu
Summary: In this study, a cobalt-catalyzed selective hydroallylation reaction was developed to synthesize branched 1,4-dienes. The reaction exhibited excellent functional group tolerance and substrate scope, allowing for gram-scale reactions. The proposed mechanism was based on deuterium labeling experiment and kinetic studies.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jianyang Dong, Fuyang Yue, Jianhua Liu, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: The described Minisci reaction allows for the catalytic synthesis of heteroarylethyl alcohols by sequentially adding H2O and N-heteroarenes across olefinic double bonds. This scalable protocol enables direct hydroxy-heteroarylation of olefins with a wide range of N-heteroarenes and has the potential to rapidly convert abundant feedstock materials into medically relevant molecules.
Article
Chemistry, Multidisciplinary
Xitao Zhang, Sheng Zhang, Shihong Li, Xiujuan Feng, Yoshinori Yamamoto, Ming Bao
Summary: This paper describes an unprecedented three-component addition reaction, which allows for the efficient synthesis of gem-dichloroalkane derivatives in mild conditions without affecting important functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Nicolas Millius, Guillaume Lapointe, Philippe Renaud
Article
Chemistry, Multidisciplinary
Emy Andre-Joyaux, Andrey Kuzovlev, Nicholas D. C. Tappin, Philippe Renaud
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Applied
Nicholas D. C. Tappin, Philippe Renaud
Summary: An improved procedure for halogen atom and chalcogen group transfer radical additions is reported, utilizing the thermal decomposition of DTBHN to produce reactive methyl radicals. This initiation method generates gaseous or volatile byproducts for easy purification, with simple reaction conditions and broad scope of application demonstrated. Additionally, an alternative source of radicals, DTBPO, is also shown to be effective under identical conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Elena Pruteanu, Nicholas D. C. Tappin, Vladilena Girbu, Olga Morarescu, Fabrice Denes, Veaceslav Kulcitki, Philippe Renaud
Summary: The modification of highly oxygenated forskolin and two less functionalized model substrates was investigated via intermolecular carbon-centered radical addition, leading to highly regio- and reasonably stereoselective iodine atom transfer radical addition reactions. Unexpected cyclic ether derivative was obtained from unprotected forskolin, while in situ protection of the 1,3-diol moiety as a cyclic boronic ester occurred during the iodine ATRA process by changing the mode of radical process initiation. This mild radical-mediated in situ protection of 1,3-diol may have broad applications in radical and non-radical transformations.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Lars Gnaegi, Remo Arnold, Florence Giornal, Harish Jangra, Ajoy Kapat, Erich Nyfeler, Robin M. Schaerer, Hendrik Zipse, Philippe Renaud
Summary: The stereoselectivity and stereospecificity of the triflate-mediated intramolecular Schmidt reaction of substituted 3-(1-azidocyclohexyl)propanol derivatives leading to octahydro-1H-pyrrolo[1,2-a]azepine has been studied. Chiral alcohols are converted to the azabicyclic derivative with limited racemization, and the diastereoselectivity is controlled by the initial asymmetric alcohol center. The concise synthesis of two alkaloids found in the venom of workers of the ant Myrmicaria melanogaster is reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Elena Pruteanu, Vladilena Girbu, Nicon Ungur, Leentje Persoons, Dirk Daelemans, Philippe Renaud, Veaceslav Kulcitki
Summary: A convenient molecular editing strategy based on radical mediated C-C bond formation has been developed for modification of available ent-kauranic natural scaffolds. The study shows that this strategy can lead to the synthesis of extended diterpenes with broad structural diversity and artificial diterpene-alkaloid hybrids, some of which exhibit significant cytotoxicity and promising selectivity indexes. These findings provide a solid foundation for further research on the synthesis of derivatives based on available natural product templates.
Article
Chemistry, Multidisciplinary
Tirtha Mandal, Shilpi Karmakar, Ajoy Kapat, Jyotirmayee Dash
Summary: A modular and flexible three-step synthetic strategy has been developed for the synthesis of acridone natural products of biological significance. The method has been successful in the efficient synthesis of acronycine and noracronycine alkaloids with improved overall yields. The synthetic utility of the present strategy has also been showcased by the synthesis of oxa and thia analogues of acronycine alkaloid.
Article
Chemistry, Multidisciplinary
Eloise Colson, Julie Andrez, Ali Dabbous, Fabrice Denes, Vincent Maurel, Jean-Marie Mouesca, Philippe Renaud
Summary: A mild and simple synthesis method using visible-light photoredox catalysis is reported in this study, which provides valuable bicyclic alkaloid skeletons with high yields and high diastereoselectivity from readily available starting materials. This method is of great significance for medicinal chemistry research.
COMMUNICATIONS CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ali Dabbous, Eloise Colson, Debargha Chakravorty, Jean-Marie Mouesca, Christian Lombard, Sylvain Caillat, Jean-Luc Ravanat, Fabien Dubois, Fabrice Denes, Philippe Renaud, Vincent Maurel
Summary: The feasibility of generating alpha-aminoalkyl free radicals using various Quantum Dots (QDs) was experimentally demonstrated. QDs such as CdS core, CdSe core, and inverted type I CdS-CdSe core-shell were found to be efficient photocatalysts for a radical [3+3]-annulation reaction, leading to the formation of tropane derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Gulsana Sissengaliyeva, Fabrice Denes, Vladilena Girbu, Veaceslav Kulcitki, Elena Hofstetter, Philippe Renaud
Summary: The direct hydroperfluoroalkylation of unactivated alkenes using iodoperfluoroalkanes and 4-tert-butylcatechol as a hydrogen source has been achieved at room temperature. Hydrotrifluoromethylation can also be achieved using gaseous trifluoromethyl iodide. Additionally, a simple two-step, one-pot hydrotrifluoromethylation process using trifluoromethanesulfonyl chloride as a trifluoromethyl radical source has been developed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Asrar Ahmad, Shakir Ali Siddiqui, Garvisha Mittal, N. Sukumar, Kshatresh Dutta Dubey, Ajoy Kapat
Summary: Applications of photochemistry are gaining popularity due to its simplicity, environmental friendliness, and economic sustainability compared to thermochemistry. Photoinduced radical polymerization (PRP) reactions are finding more biological applications, especially in dental restoration, tissue engineering, and artificial bone generation. A new efficient co-initiator has been designed and synthesized for a PRP reaction via a barrierless sequential conjugate addition reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Luca Vedani, Manuel Gnagi-Lux, Fabrice Denes, Philippe Renaud
Summary: In this study, the preparation of polysubstituted bicyclo[3.1.0]hexanes from substituted pent-4-en-1-ylboronic acid esters was investigated. The key steps involve Matteson homologation and intramolecular cyclopropanation. By converting pinacol boronic esters to catechol boronic esters, enantioenriched bicyclo[3.1.0]hexanes can be synthesized using chiral-auxiliary control or sparteine-controlled enantioselective boroalkylation of alcohols.
Article
Chemistry, Multidisciplinary
Samuel Rieder, Camilo Melendez, Fabrice Denes, Harish Jangra, Kleni Mulliri, Hendrik Zipse, Philippe Renaud
Summary: The study describes the monoalkylation of N-methoxypyridinium salts with alkyl radicals generated from alkenes, alkyl iodides, and xanthates. The reaction proceeds under neutral conditions without the need for external oxidants, demonstrating high reactivity of methoxypyridinium salts towards radicals. It has been applied for the synthesis of unique pyridinylated terpenoids and extended to a three-component carbopyridinylation of electron-rich alkenes.
Article
Chemistry, Multidisciplinary
Qi Huang, Sankar Rao Suravarapu, Philippe Renaud
Summary: A general method has been developed for the hydroalkylation of electron-rich alkenes, showing high efficacy due to favorable polar effects and achieving good stereoselectivity control in chiral compounds.
