Article
Chemistry, Multidisciplinary
Lilla Koser, Vivian Miles Lechner, Thorsten Bach
Summary: The first chemical total synthesis of the highly oxygenated polyketide enterocin has been achieved using a late-stage biomimetic reaction cascade. The synthesis involved assembling a pivotal precursor from three readily available building blocks, with a chiral dithioacetal representing the core fragment. Additional building blocks were attached to both ends of the core fragment through aldol reactions, leading to the installation of four stereogenic centers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Kosuke Okada, Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: The synthesis of (+)-pleiocarpamine, (+)-voacalgine A and (+)-bipleiophylline was achieved in this study. The 10-step synthesis of (+)-pleiocarpamine features the construction of stereochemistry at the C16 position by radical cyclization and the synthesis of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C-H functionalization. By modifying the biomimetic aerobic oxidative coupling of tryptophane derivatives catalyzed by FePc(CO2H)(8), the oxidative coupling of (+)-pleiocarpamine with pyrocatechuic acid produced (+)-voacalgine A. The total synthesis of (+)-bipleiophylline was completed by the second coupling of (+)-voacalgine A with (+)-pleiocarpamine or the one-pot couplings of 2 equiv of (+)-pleiocarpamine with pyrocatechuic acid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Nicolo Fontana, Noel Angel Espinosa-Jalapa, Michael Seidl, Jonathan O. Bauer
Summary: This study presents an efficient methodology for the synthesis of new Si-chiral four-membered CPSSi* heterocyclic cations, elucidates the stereochemical sequence and mechanisms involved, and demonstrates the ease of achieving chemoselectivity switch through slight modifications of the solvent. The intermolecularity of the reaction was supported by various experiments and quantum chemical calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
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)
Article
Chemistry, Organic
Laura Burchill, Aaron J. Day, Oussama Yahiaoui, Jonathan H. George
Summary: Total synthesis of the Rhododendron meroterpenoids rubiginosins A and G, which possess unusual 6-6-6-4 ring systems, has been achieved using a bioinspired cascade approach. Stepwise synthesis of these natural products, and the related 6-6-5-4 meroterpenoids fastinoid B and rhodonoid B, from naturally occurring chromene precursors is also reported.
Article
Chemistry, Organic
Nicolas S. S. George, Marharyta Kosiuha, Alexandre Moquette, Christophe Parsy
Summary: We describe a versatile methodology for the synthesis of 1,2-sulfoximidoyl ethanols through a regioselective epoxide ring-opening reaction. The chemoselectivity of the reaction is assessed by competition reactions with other nucleophiles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tushar M. Khopade, Kalyani Ajayan, Dona Mariya Vincent, Amy L. Lane, Rajesh Viswanathan
Summary: The research team successfully synthesized a derivative of the natural product nocardioazine B using a biomimetic approach, achieving high yield. This derivative exhibits potential as a treatment for multidrug-resistant cancer cells, offering a new strategy against resistant carcinomas. Additionally, this synthesis method provides direct access to related natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Thomas Mies, Andrew J. P. White, Philip J. Parsons, Anthony G. M. Barrett
Summary: This study describes the synthesis of a range of hongoquercins using gold-catalyzed enyne cyclization reactions, and the preparation of the parent enyne resorcylate precursors through several steps including regioselective acylation, Tsuji-Trost allylic decarboxylative rearrangement, and aromatization. The dioxinone keto ester was prepared in 6 steps from geraniol through allylic functionalization and alkyne synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(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)
Article
Chemistry, Multidisciplinary
Luis Werner, Julika Hagn, Janis Walpuski, Udo Radius
Summary: This study synthesized aminoborate complexes using N-heterocyclic carbene ligands and assessed their potential applications in catalytic CO2 conversion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Ming-Xiang Li, Bing-Chao Yan, Min Zhou, Xing-Ren Li, Xiao-nian Li, Shi-Jun He, Han-Dong Sun, Pema-Tenzin Puno
Summary: The structures of two new organic compounds, (+)-Isoscopariusins B (1) and C (2), with a 6/6/4 tricyclic carbon skeleton and seven continuous stereocenters, were determined and confirmed through nuclear magnetic resonance analysis and biomimetic synthesis using readily available alkene 5. The construction of a cyclobutane core with four stereogenic centers was achieved by an intermolecular [2+2] photocycloaddition with cooperative catalysis of a Lewis acid and an Ir photocatalyst.
Article
Chemistry, Multidisciplinary
Marko Nesic, David B. Ryffel, Jonathan Maturano, Michael Shevlin, Scott R. Pollack, Donald R. Gauthier Jr, Pablo Trigo-Mourin, Li-Kang Zhang, Danielle M. Schultz, Jamie M. McCabe Dunn, Louis-Charles Campeau, Niki R. Patel, David A. Petrone, David Sarlah
Summary: The collaborative total synthesis of darobactin A, a selective antibiotic against Gram-negative bacteria, has been achieved in a convergent manner using D-Garner's aldehyde and L-serine as starting materials. The synthesis involved 16 steps and three scalable routes were developed to synthesize non-canonical amino acids. The closure of the bismacrocycle was successfully achieved through sequential, halogen-selective Larock indole syntheses, with the cyclization order playing a crucial role in the formation of the desired atropisomer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Jonathan H. George
Summary: Natural products are biosynthesized using a limited pool of starting materials, while biomimetic total synthesis attempts to replicate predisposed pathways using chemical reagents. By avoiding the use of protecting groups, researchers aim to explore the innate reactivity of biosynthetic intermediates. Biomimetic synthesis is often concise and efficient, following atom, step, and redox economies of synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Abdus Salam, Dileep Kumar, Tonish Kumar Sahu, Rahimuddin Khan, Tabrez Khan
Summary: In this study, a unified approach for the enantioselective total synthesis of magnoshinin and merrilliaquinone is reported. The key feature of the synthesis is the late-stage oxidative functionalization of the chiral tetralin core using relayed asymmetric induction strategy and DDQ assistance. The chemoselective redox chemistry enables the synthesis of (-)-magnoshinin (28.2% overall yield) and (+)-merrilliaquinone (20.6% overall yield) starting from a known compound.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kyle J. Cassaidy, Viresh H. Rawal
Summary: This paper reports a new total synthesis strategy utilizing the transition metal-catalyzed [2 + 2 + 2] cycloisomerization reaction, achieving the first total synthesis of a member from the Veratrum alkaloids family.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
