Article
Chemistry, Organic
Fang Xie, Jie Zhao, Deyue Ren, Jianming Xue, Jingyi Wang, Qin Zhao, Lu Liu, Xiaodan Liu
Summary: A Cu-catalyzed coupling reaction between cyclic imino esters and 2H-azirines has been developed, allowing for the synthesis of novel optically active aziridines in high yields and with excellent levels of diastereo- and enantioselectivities under mild conditions. This method features a broad substrate scope, good functional group compatibility, and enriches the existing reaction type for the rapid synthesis of optically active aziridines bearing vicinal tetrasubstituted stereogenic carbon centers.
Review
Chemistry, Organic
D. H. Sreenivasa Rao, Ayon Chatterjee, Santosh Kumar Padhi
Summary: Chiral beta-nitroalcohols are important building blocks in organic synthesis, and biocatalytic methods have gained significant importance for their asymmetric synthesis. Different biocatalytic strategies, such as kinetic resolution and Henry reaction, have been developed for the asymmetric synthesis of beta-nitroalcohol stereoisomers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Hyun Ji Jeon, Su Min Park, Yu Lim Lee, Sang-gi Lee
Summary: The palladium-catalyzed divergent asymmetric synthesis of chiral spiro-furanindoline derivatives is described. The zwitterionic alkoxy pi-allyl Pd(II) intermediate, generated catalytically from vinyl ethylene carbonate (VEC), could undergo ligand-controlled enantio-and diastereoselective dipolar [3 + 2] spiroannulation with indole-based azadienes to afford the optically active spiro-furanindolines embedding an all-carbon quaternary stereocenter in high yields (up to 99%) with good to excellent stereoselectivities (up to 99% ee and up to >94:6 dr).
Article
Multidisciplinary Sciences
He Yang, Wenjun Tang
Summary: In this paper, researchers have developed a general, efficient, and enantioselective synthesis of axially chiral biaryl structures with ortho sulfur or nitrogen substituents using asymmetric cross-coupling. The method shows excellent compatibility with various functional groups and structural features, allowing for the synthesis of diverse chiral biaryl structures with high synthetic value. The authors have also demonstrated the applicability of the method in the synthesis of bioactive molecules and chiroptical molecules with circularly polarized luminescence properties.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Nasir Tajuddeen, Doris Feineis, Heiko Ihmels, Gerhard Bringmann
Summary: The naphthylisoquinoline (NIQ) alkaloids are a class of natural biaryls with diverse structures, biosynthetic pathways, and pharmacological properties. The synthesis of these compounds is challenging, with the stereocontrolled construction of the biaryl bond as a key step. This review focuses on the synthesis of NIQs with a stable biaryl axis, emphasizing the preparation of atropisomers. Internal and external asymmetric inductions, as well as innovative approaches, are discussed in detail.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Lu Chen, Kejing Xie, Jingyang Zhang, Liansuo Zu
Summary: This paper reports a direct spirocyclization approach for the chemical synthesis of spiro[cyclohexane-2-indoline] alkaloids. The absolute stereochemistry was introduced by a desymmetrizing Dieckmann condensation, and the relative stereochemistry was controlled by manipulating the kinetic and thermodynamic pathways of the spirocyclization. It is demonstrated that a common lactone-type intermediate, rather than the proposed diester-type alkaloid precursor, can bridge the chemical synthesis of this class of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ming Wu, Yi-Wei Chen, Qian Lu, Yong-Bin Wang, Jun Kee Cheng, Peiyuan Yu, Bin Tan
Summary: A highly efficient method for the synthesis of atropisomers through functionalization of the Si-C bond between dinaphthosiloles and silanol nucleophiles was presented. The versatile nature of the Si-C bond allows for the facile derivatization of chiral products into other functional atropisomers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ming Wu, Yi-Wei Chen, Qian Lu, Yong-Bin Wang, Jun Kee Cheng, Peiyuan Yu, Bin Tan
Summary: Chiral organosilanes are important chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. An efficient method for atroposelective synthesis of biaryl siloxane atropisomers via organocatalytic Si-C bond functionalization of dinaphthosiloles with silanol nucleophiles is presented. The reaction proceeds through an asymmetric protonation and simultaneous Si-C bond cleavage/silanolysis sequence in the presence of a newly developed chiral Bronsted acid catalyst. The versatile nature of the Si-C bond expands the applicability of this method.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Ankit Kumar, Hiroaki Sasai, Shinobu Takizawa
Summary: In this article, the use of vanadium catalyst in coupling reactions for the synthesis of chiral molecules is summarized. Various chiral compounds, such as biarenol derivatives and polycyclic biphenols, can be synthesized using vanadium catalysts. These catalysts exhibit high activity and stereoselectivity, tolerate various functional groups, and avoid overoxidation of coupling products.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Chiara Portolani, Giovanni Centonze, Sara Luciani, Andrea Pellegrini, Paolo Righi, Andrea Mazzanti, Alessia Ciogli, Andrea Sorato, Giorgio Bencivenni
Summary: The first catalytic enantioselective and diastereoselective synthesis of atropisomeric hydrazides was achieved using a sequential catalysis protocol, providing a stereodivergent approach to enantioenriched atropisomeric hydrazides. The resulting axially chiral hydrazides were obtained directly from commercially available reagents in high yields and with good stereocontrol, demonstrating the effectiveness of this strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Ankit Kumar, Hiroaki Sasai, Shinobu Takizawa
Summary: This paper summarizes the applications of vanadium-catalyzed coupling reactions in the synthesis of chiral compounds and their mechanisms.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Cheng Sheng, Zheng Ling, Junzhe Xiao, Kai Yang, Xie Fang, Shengming Ma, Wanbin Zhang
Summary: In this study, enantio- and diastereoselective α-additions of 1-alkynyl ketimines with dual-copper-catalysis were successfully achieved under mild conditions, leading to the synthesis of chiral tetrasubstituted α-amino allenoates bearing a vicinal all-carbon quaternary stereocenter in high yields (up to 99% yield) with excellent enantioselectivities (up to 99% ee) and diastereoselectivities (up to >20:1 dr). The stereodivergent synthesis of the products was realized by the asymmetric α-addition reaction and the Grignard reagent promoted epimerization. Importantly, the reaction could be smoothly scaled up and applied to introduce chiral tetrasubstituted allenyl moieties into bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jinping Yuan, Pankaj Jain, Jon C. Antilla
Summary: The catalytic asymmetric addition of beta,gamma-substituted allylboronates to aldehydes has been described, showing highly efficient and selective reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xue Zhang, Shunian Li, Wenjing Yu, Yufang Xie, Chen-Ho Tung, Zhenghu Xu
Summary: An Ir(I)/squaramide cooperative catalytic strategy has been developed for the atroposelective synthesis of axially chiral aryltriazoles. This strategy allows the synthesis of structurally novel aryltriazole skeletons that cannot be obtained by traditional click reactions, with good yields and excellent enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Alemayehu Gashaw Woldegiorgis, Haorui Gu, Xufeng Lin
Summary: The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were used to synthesize axially chiral styrenes connected to an axially chiral naphthyl-indole unit. By employing chiral phosphoric acid as the catalyst, these axially chiral styrenes were obtained in good yields (up to 96%) and excellent stereoselectivity (up to >99.9% ee, >20:1 dr, and >99:1 E/Z) under mild conditions. Furthermore, further synthetic transformations were achieved with high yields and excellent stereocontrol.
Article
Chemistry, Organic
Michel Chiarucci, Andrea Mazzanti, Paolo Righi, Giorgio Bencivenni, Michele Mancinelli
Summary: A series of 1,8-bis(1-naphthyl)-naphthalenes with different substituents have been synthesized to investigate noncovalent interactions between stacked arenes. DFT calculations, NMR, and ECD experiments were used to determine the best geometries and understand the role of dispersive and electrostatic contributions. The study revealed that electrostatic contributions greatly influence the interaction energy of the two naphthyl rings, while dispersive forces play a minor role in determining the parallel displaced geometry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Nicolo Tampellini, Paolo Righi, Giorgio Bencivenni
Summary: A computational study using density functional theory was conducted to understand the mechanism of atroposelective desymmetrization of N-(2-t-butylaryl)maleimide catalyzed by 9-amino(9-deoxy) epi-quinine. The results showed that the atroposelectivity was achieved through steric and dispersion interactions of the catalyst. The crucial role of N-Boc-L-Ph-glycine was identified in forming a closed transition-state geometry and activating the reaction partners.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Antonia Iazzetti, Giulia Mazzoccanti, Giorgio Bencivenni, Paolo Righi, Andrea Calcaterra, Claudio Villani, Alessia Ciogli
Summary: The field of organocatalysis is expanding rapidly, with a focus on understanding mechanisms of reaction and catalytic processes. A thorough study using ESI-MS spectrometry of amino-organocatalyzed reactions has provided insights into the complex pathways involved.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chiara Portolani, Giovanni Centonze, Sara Luciani, Andrea Pellegrini, Paolo Righi, Andrea Mazzanti, Alessia Ciogli, Andrea Sorato, Giorgio Bencivenni
Summary: The first catalytic enantioselective and diastereoselective synthesis of atropisomeric hydrazides was achieved using a sequential catalysis protocol, providing a stereodivergent approach to enantioenriched atropisomeric hydrazides. The resulting axially chiral hydrazides were obtained directly from commercially available reagents in high yields and with good stereocontrol, demonstrating the effectiveness of this strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jacopo De Maron, Tommaso Tabanelli, Francesca Ospitali, Carlos Lopez Cruz, Paolo Righi, Fabrizio Cavani
Summary: For the first time, the continuous-flow, gas-phase oxidative dehydrogenation (ODH) of an actual mixture of decen-1-ol isomers (Isorosalva alcohol) towards the corresponding mixture of aldehydes (Costenal analogues, valuable ingredients in perfumes formulation) was achieved over noble metal-free catalysts. The optimized reaction conditions over a copper ferrite (Cu/Fe/O) and the characterization of the catalytic material revealed the important role of well dispersed copper oxide over a Fe-enriched spinel in promoting the selective ODH of Isorosalva alcohol. The high dispersion of Cu over the support and the cooperative effect between Cu and Fe species were identified as the main factors for the superior catalytic activity and selectivity of CuO/gamma-Fe2O3.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Giovanni Centonze, Chiara Portolani, Paolo Righi, Giorgio Bencivenni
Summary: Axially chiral compounds, once viewed as merely a laboratory curiosity, have gained recognition in the past two decades for their significant role in medicinal, biological, and material chemistry. The asymmetric synthesis of atropisomers, particularly N-N atropisomers, has become a rapidly expanding field with new challenges and frontiers. This review highlights recent advances and breakthroughs in the enantioselective synthesis of N-N atropisomers, showcasing the strategies and frameworks involved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
