Article
Chemistry, Multidisciplinary
Haoran Dong, Dachao Hu, Benke Hong, Jin Wang, Xiaoguang Lei
Summary: The first total syntheses of four natural antibiotics, vermisporin, PF1052/AB4015-A, AB4015-L, AB4015-B, and one hydrogenated natural product derivative, AB4015-A2, featuring a tetramic acid bearing cis-decalin ring, are reported. The functionalized cis-decalin ring was constructed via a diastereoselective intramolecular Diels-Alder (IMDA) reaction, with a rare endo-boat transition state. The efficient installation of the sterically hindered epoxy group in vermisporin, PF1052/AB4015-A, and AB4015-L was achieved through an intramolecular neighboring-group-oriented strategy, and the desired tetramic acid structure was obtained through a one-pot aminolysis/Dieckmann condensation cascade using L-amino acid derivatives. The total synthesis allowed for the unequivocal verification of the absolute configuration of these natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dongshan Wu, Xiaoguang Lei
Summary: Enzymatic cascade reactions are powerful technologies for synthesizing natural products and valuable molecules in an environmentally friendly and cost-effective manner. Single-Enzyme-Catalyzed Cascade reactions (SECC) significantly improve synthesis efficiency. This digest highlights recent inspiring examples of SECC in synthesizing natural products and natural product-like molecules, with a focus on their unique advantages.
Review
Chemistry, Multidisciplinary
Debobrata Paul, Ashis Kundu, Sanu Saha, Rajib Kumar Goswami
Summary: This feature article highlights total synthesis as a reliable tool for confirming the structure of natural products. Despite advances in spectroscopic techniques, structural misassignments of natural products remain common. Recent case studies have shown that chemical synthesis can be used to revise the structures of natural products.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yongkang Li, Dan E. Wise, Joshua K. Mitchell, Marvin Parasram
Summary: We present a new method for the synthesis of phenanthrenes from aryl iodides and styrenes through a photoinduced arylation/cyclization cascade. This approach eliminates the use of hazardous reagents and allows for the formation of unsymmetrical phenanthrenes with good tolerance towards different functional groups. Mechanistic studies have revealed that photoexcitation of aryl iodides leads to cleavage of the C-I bond, followed by aryl radical species formation and subsequent cyclization promoted by in situ generated iodine.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wei Cao, Zhen Wang, Yan Hao, Tianli Wang, Shaomin Fu, Bo Liu
Summary: We have achieved the total synthesis of sculponin U, a polycyclic C-20-oxygenated kaurane diterpenoid, through a radical cascade cyclization induced by photoinduced electron transfer (PET) of a silyl enolate. Our synthetic strategy involved a Diels-Alder reaction to form the middle six-membered ring and an iron-catalyzed hydrogen atom transfer to close the western cyclohexane ring. The successful preparation of enantiopure silyl enolate as the PET precursor allows for the asymmetric total synthesis of sculponin U and provides a new approach for the synthesis of structurally related compounds and pharmaceutical derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yunpeng Ji, Benke Hong, Ivan Franzoni, Mengyang Wang, Weiqiang Guan, Hongli Jia, Houhua Li
Summary: In this paper, a 9-step enantioselective total synthesis of (+)-hyperforin and (+)-pyrohyperforin was described, starting from commercially available allylacetone. The synthesis involved important reactions such as the enantioselective deconjugative alpha-alkylation using chiral lithium amides as stereodirecting auxiliaries, the HfCl4-mediated carbonyl alpha-tert-alkylation to form the intricate bicyclo[3.3.1]nonane framework, an abiotic cascade pyran formation, and a selective 1,4-semihydrogenation of polyenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Lisa-Catherine Rosenbaum, Maximilian Haefner, Tanja Gaich
Summary: A racemic and scalable enantioselective total synthesis of (+)-waihoensene was achieved, featuring an angular triquinane substructure with an all-cis-fused tetracyclic backbone and six contiguous stereocenters, four of which are quaternary. Enantioselectivity was introduced at an early stage, and key structural features were efficiently installed through several diastereoselective reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Zhen Yang
Summary: The total synthesis endeavors contribute to the discovery and invention of new synthetic reactions to advance organic synthesis. Bioactive compounds share common features, such as molecular complexity, protein-binding ability, structural rigidity, and three-dimensionality. Total synthesis offers an alternative solution for generating scarce natural products and their derivatives for studying their biological functions.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Xikang Zheng, Yan Li, Mengtie Guan, Lingyue Wang, Shilong Wei, Yi-Cheng Li, Chin-Yuan Chang, Zhengren Xu
Summary: A unified strategy for the biomimetic total synthesis of the spiroindimicin family of natural products was reported. Key transformations include one-pot two-enzyme-catalyzed oxidative dimerization and regioselective bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Tayebeh Momeni, Vahideh Zadsirjan, Mohammad Meshkatalsadat, Mohammadali Pourmohammadi-Mahunaki
Summary: This review presents the application of cobalt-catalyzed reactions in the synthesis of biologically active natural products from 2000 to date.
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Chemistry, Applied
Elisa Vignali, Loredano Pollegioni, Giovanna Di Nardo, Francesca Valetti, Silvia Gazzola, Gianfranco Gilardi, Elena Rosini
Summary: This study reported the first multi-enzymatic, one-pot bioconversion process of vanillin into ccMA, achieving high yield in a lab-scale procedure within 30 hours. This research demonstrates a sustainable alternative for producing high value added products from renewable resources.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yusuke Imamura, Kyohei Takaoka, Yuma Komori, Masanori Nagatomo, Masayuki Inoue
Summary: This study presents a 34-step synthesis of Taxol, involving inter- and intramolecular radical reactions to connect the A- and C-ring fragments and cyclize the B-ring. The A- and C-ring functional groups were then efficiently modified using newly developed selective reactions. The construction of the D-ring and its conjugation with the beta-amino acid led to the successful synthesis of Taxol. This synthesis provides useful insights for the design of multistep syntheses of diverse bioactive natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Quentin Ronzon, Wei Zhang, Thomas Charote, Nicolas Casaretto, Gilles Frison, Bastien Nay
Summary: This study describes the total synthesis of two fungal cyclotripeptides, (+)-cinereain and (-)-janoxepin, which possess a complex heterocyclic core and exhibit interesting phytotoxic and antimalarial activities. The key step in the synthesis is a one-pot cascade reaction that releases a reactive spiro[2-vinylcyclopropane-1,5'-pyrimidine-4',6'-dione] intermediate through the cyclocondensation of two fragments. This intermediate undergoes a spontaneous retro-Claisen rearrangement, leading to the formation of a 2,5-dihydrooxepin-fused heterocyclic product. The challenging oxepin ring is finally forged through a palladium-catalyzed beta-hydride elimination of an allylic fluoride intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ze-Jun Xu, Xu-Yuan Liu, Ming-Zhu Zhu, Yu-Liang Xu, Yue Yu, Hai-Ruo Xu, Ai-Xia Cheng, Hong-Xiang Lou
Summary: In this study, two types of photoredox-catalyzed cascade reactions using diaryliodonium salts were developed for the concise synthesis of norascyronone A and beta-eudesmol. A rationally designed photoredox-catalyzed arylation/cyclization/Friedel-Crafts cascade reaction was used for the norascyronone synthesis, while a visible-light-induced radical cyclization/acyloxy-migration reaction was explored for the eudesmol synthesis, with mechanistic studies indicating initiation by one-electron oxidation of the enol ester.
