Article
Multidisciplinary Sciences
Zishuo Zhang, Jintong Zhang, Quan Gao, Yu Zhou, Mingyu Yang, Haiqun Cao, Tingting Sun, Gen Luo, Zhi-Chao Cao
Summary: The study demonstrates a C(sp3)-C(sp2) cross-coupling via asymmetric activation of the aromatic C-O bond for the synthesis of alkylated, axially chiral biaryl compounds. This method offers promising potential for complex molecule synthesis and asymmetric catalysis through nickel catalysis with good enantiocontrol.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Nicholas E. Bode, Ryan T. McGuire, Mark Stradiotto
Summary: In this study, an effective catalyst system, PhPAd-DalPhos/NiCOD2, was identified and applied for the O-arylation of substituted phenols with chloropyridine-type electrophiles under thermal conditions, leading to pyridyl-O-aryl frameworks that are present in active pharmaceutical ingredients.
Review
Chemistry, Multidisciplinary
Xiaobo Pang, Pei-Feng Su, Xing-Zhong Shu
Summary: Transition-metal-catalyzed reductive coupling of electrophiles is a powerful method for constructing molecules. This review summarizes recent research in our laboratory on this topic, focusing on reactions involving readily available, low-cost, stable but unreactive electrophiles. The findings include deoxygenative C-C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C-Si coupling of chlorosilanes, and reductive C-Ge coupling of chlorogermanes.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Xiaobo Pang, Pei-Feng Su, Xing-Zhong Shu
Summary: Transition-metal-catalyzed reductive coupling of electrophiles has become a powerful tool for constructing molecules. This article summarizes recent research findings in our laboratory, focusing on reactions involving more readily available, low-cost, and stable but unreactive electrophiles. These findings include deoxygenative C-C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C-Si coupling of chlorosilanes, and reductive C-Ge coupling of chlorogermanes.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Emily K. Reeves, Emily D. Entz, Sharon R. Neufeldt
Summary: Chemodivergent cross-couplings refer to reactions in which one potentially reactive functional group can be made to react based on choice of conditions. Factors influencing selectivity include catalyst ligation state, solvent polarity, and metal identity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Editorial Material
Chemistry, Organic
Chengwei Liu, Michal Szostak
Summary: The decarbonylative Sonogashira cross-coupling reaction utilizes carboxylic acids as substrates to produce arylalkynes, offering a novel synthetic avenue.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Chao Li, Liang Ling, Zheng Luo, Sha Wang, Xiaoyu Zhang, Xiaoming Zeng
Summary: In this study, a deoxygenative cross-coupling reaction between unactivated aryl esters and unsaturated amides was achieved using chromium catalysis. The reaction involves cleavage of C-O bonds by Cr and subsequent silylation, leading to the formation of arylated silachromate that undergoes reductive elimination and deoxygenative hydrogen transfer to cross-couple with carbonyls of amides. This method offers a strategy for the synthesis of pharmaceutically relevant diarylmethylated amines.
Article
Chemistry, Physical
Chao Li, Liang Ling, Zheng Luo, Sha Wang, Xiaoyu Zhang, Xiaoming Zeng
Summary: In this study, we report a deoxygenative cross-coupling reaction between unactivated aryl esters and unsaturated amides, enabled by chromium catalysis. Mechanistic studies indicate that ester C-O cleavage by Cr and subsequent silylation leads to the formation of arylated silachromate, which regioselectively adds to carbonyls of amides through reductive elimination and deoxygenative hydrogen transfer. This reaction provides a strategy for the synthesis of pharmaceutically interesting diarylmethylated amines.
Article
Chemistry, Multidisciplinary
Longlong Xi, Liting Du, Zhuangzhi Shi
Summary: A nickel-catalyzed reductive cross-coupling reaction has been reported for the synthesis of substituted fluoroarenes through chelation-assisted C-F activation of polyfluoroarenes and alkyl electrophiles. The method shows excellent regioselectivity and can be applied to various primary and secondary alkyl (pseudo)halides.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Shiyi Yang, Hengzhao Li, Xiang Yu, Jie An, Michal Szostak
Summary: A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using a very low loading of [Pd] in the presence of mild K3PO4 base under aqueous conditions. This operationally trivial protocol allows for the activation of C-O bond and is tolerant to various sensitive functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Liangliang Zhang, Martin Oestreich
Summary: A new nickel/zinc-catalyzed cross-electrophile coupling reaction has been reported, utilizing alkyl electrophiles activated by an alpha-cyano group and chlorosilanes. Elemental zinc serves as the stoichiometric reductant in this reductive coupling process, allowing for the formation of a C(sp(3))-Si bond starting from two electrophilic reactants. This method differs from previous approaches that rely on the combination of carbon nucleophiles and silicon electrophiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Raymond F. Turro, Julie L. H. Wahlman, Z. Jaron Tong, Xiahe Chen, Miao Yang, Emily P. Chen, Xin Hong, Ryan G. Hadt, K. N. Houk, Yun-Fang Yang, Sarah E. Reisman
Summary: Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of N-hydroxyphthalimide (NHP) esters and benzylic chlorides were conducted. The study revealed divergent mechanisms for these related transformations, with the mechanism of C(sp(3)) activation changing depending on the reactants used. Kinetic experiments showed that the rate of NHP ester reduction can be tuned by changing the Lewis acid. Spectroscopic studies and DFT calculations provided insights into the catalyst resting state and the origin of enantioinduction for the Ni-BOX catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ziqi Zhu, Lin Lin, Jieshuai Xiao, Zhuangzhi Shi
Summary: The stereo- and enantioselective cross-electrophile coupling involving C-F bond activation was successfully achieved using a chiral nickel complex and B(2)pin(2) as a stoichiometric reductant. The reaction allows the construction of a C(sp(2))-C(sp(3)) bond under mild conditions, resulting in a variety of monofluoroalkenes bearing stereogenic allylic centers. Initial mechanistic studies suggest a radical chain pathway may be involved in the C-F bond activation process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhenghong Zhou, Jimin Yang, Bo Yang, Yang Han, Lijuan Zhu, Xiao-Song Xue, Feng Zhu
Summary: This study presents a pioneering example of nickel-catalysed enantioconvergent Stille cross-coupling reactions. The reactions result in the formation of C-C bonds in good to high yields with excellent stereoselectivity, providing a practical and cost-effective method for synthesis. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process, opening up new research possibilities in the field of Stille reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nektarios Kranidiotis-Hisatomi, Hong Yi, Martin Oestreich
Summary: A two-step sequence for the enantio- and diastereoselective synthesis of exclusively alkyl-substituted acyclic allylic systems with a stereocenter in the allylic position is reported, where asymmetric induction and site selectivity are controlled in a nickel-catalyzed reaction. The silyl group plays a key role in steering allylic displacement towards formation of a vinylsilane regioisomer, facilitating installation of various C(sp(3)) substituents in a subsequent step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Yanlin Shi, Sung-Po R. Chen, George Fragkiadakis, Daniele Parisi, Virgil Percec, Dimitris Vlassopoulos, Michael J. Monteiro
Summary: The shape, breadth, and average molecular weight of the overall molecular weight distribution (MWD) are important for determining polymer properties. Traditional methods can only achieve desired Gaussian distribution through complex modeling, while living radical polymerization provides a simpler route. Blending low-reactive RAFT agents allows the construction of square, slanted, and chair-like MWDs, providing control over MWD shape and breadth. This blending method overcomes difficulties in producing unusual MWDs and offers a general synthetic strategy for studying structure-property relationships of polymers.
Article
Polymer Science
Devendra S. Maurya, Jasper Adamson, Nabil Bensabeh, Gerard Lligadas, Virgil Percec
Summary: DMSO is an interesting solvent for copper-catalyzed living radical polymerization due to its ability to provide high conversion and absence of termination. Although it is not the most efficient solvent for disproportionation of Cu(I)X, DMSO allows for the development of complex-architecture methodologies by living and immortal polymerizations. The mechanism behind this precision is currently being investigated.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Virgil Percec, Dipankar Sahoo, Jasper Adamson
Summary: This article organized for the first time the stimuli-responsive principles of supramolecular organizations emerging from self-assembling and self-organizable dendrons, dendrimers, and dendronized polymers, which is fundamental to natural and life sciences.
Article
Polymer Science
Adrian Moreno, Gerard Lligadas, Jasper Adamson, Devendra S. Maurya, Virgil Percec
Summary: The Nobel Prize in Chemistry for 2022 was awarded to Bertozzi, Meldal, and Sharpless for their contribution to the development of click chemistry and biorthogonal chemistry. Since 2001, when click chemistry was proposed by Sharpless's laboratory, synthetic chemists have favored click reactions as a preferred method to create new functions. This perspective summarizes the research conducted in our laboratories on CuAAC, TBC, and TERMINI click reactions, and their applications in assembling complex macromolecules and self-organizations with biological relevance.
Article
Pharmacology & Pharmacy
Juncheng Lu, Elena N. Atochina-Vasserman, Devendra S. Maurya, Muhammad Irhash Shalihin, Dapeng Zhang, Srijay S. Chenna, Jasper Adamson, Matthew Liu, Habib Ur Rehman Shah, Honey Shah, Qi Xiao, Bryn Queeley, Nathan A. Ona, Erin K. Reagan, Houping Ni, Dipankar Sahoo, Mihai Peterca, Drew Weissman, Virgil Percec
Summary: The use of viral and synthetic vectors for nucleic acid delivery is crucial for the rapid development of effective COVID-19 vaccines. Lipid nanoparticles (LNPs) composed of phospholipids, PEG-conjugated lipids, cholesterol, and ionizable lipids have been employed as the leading nonviral delivery vector for COVID-19 mRNA vaccines by BioNTech/Pfizer and Moderna. In this study, a methodology involving screening libraries was used to discover the molecular design principles necessary for targeted mRNA delivery to specific organs, using a one-component ionizable multifunctional amphiphilic Janus dendrimer (IAJD) derived from plant phenolic acids. These design principles simplify the synthesis of IAJDs and the assembly of monodisperse dendrimersome nanoparticles (DNPs) with predictable dimensions, ultimately enhancing accessibility to diverse mRNA-based vaccines and nanotherapeutics.
Article
Chemistry, Multidisciplinary
Dipankar Sahoo, Emad Aqad, Mihai Peterca, Virgil Percec
Summary: This publication reports the structural analysis of the 3D self-organizations of HATn molecules, revealing the formation of highly ordered helical and nonhelical pyramidal and discotic columns. It demonstrates that a single building block can self-organize into different assemblies via its constitutional isomers. The findings raise important questions about the current understanding of helical self-organizations.
Article
Chemistry, Multidisciplinary
Dipankar Sahoo, Emad Aqad, Mihai Peterca, Virgil Percec
Summary: The molecular structures of 3D crystal and 2D liquid crystal phases of discotic molecules have never been determined at the molecular level. This study investigates the molecular structure of HATn self-organizations and presents the molecular structures of HAT4 in its crystal and liquid crystal states.
Article
Chemistry, Multidisciplinary
Marc Pala, Hafssa El Khannaji, Manuela Garay-Sarmiento, Juan Carlos Ronda, Virginia Cadiz, Marina Galia, Virgil Percec, Cesar Rodriguez-Emmenegger, Gerard Lligadas
Summary: This research reports a green method for upgrading chemicals of the lactic acid portfolio into water-soluble acrylic polymers, utilizing lactate-derived solvents and Cu(0)-mediated living radical polymerization. The resulting polymers exhibit excellent biocompatibility and thermal responsiveness, forming a new family of hydrogels.
Article
Chemistry, Multidisciplinary
Virgil Percec, Dipankar Sahoo
Summary: The discovery of thermotropic liquid crystal phases self-organized from planar disc-like molecules led to the investigation of different forms of supramolecular structures. The newly discovered liquid crystal phases include helical columnar hexagonal phases from crown-like molecules, Frank-Kasper A15 phase, sigma phase, 12-fold quasi liquid crystals, and complex bundles of supramolecular columnar hexagonal arrays derived from supramolecular orientational memory. Chandrasekhar made significant contributions to the discovery of self-assembling dendrons and dendrimers through his biaxial nematic liquid crystal concept.
Article
Chemistry, Multidisciplinary
Mihai Peterca, Dipankar Sahoo, Mohammad R. Imam, Qi Xiao, Virgil Percec
Summary: This article introduces the structural simplicity and versatility of the first generation self-assembling dendron, which shows potential in investigating helical self-organization and supramolecular polymerization.
Article
Chemistry, Multidisciplinary
Mihai Peterca, Mohammad R. Imam, Andres E. Dulcey, Kentaro Morimitsu, Qi Xiao, Devendra S. Maurya, Virgil Percec
Summary: The primary structure affects the tertiary structure and determines the function. This study investigates the effect of molecular parameters on the hierarchical self-organization of self-assembling dendrons and demonstrates that hydrogen bonding can enhance the order of helical columns. The findings provide insight into the mechanisms of self-assembly and may contribute to the development of new functional materials.
Article
Chemistry, Multidisciplinary
Mohammad R. Imam, Mihai Peterca, Qi Xiao, Virgil Percec
Summary: A library of triphenylene dendronized with self-assembling dendrons via a diethylene glycol linker was synthesized and showed different self-organizations, including hexagonal columnar, Frank-Kasper, and soft quasicrystal assemblies. The presence of the diethylene glycol linker affected phase transitions and isotropization temperatures, and induced strong pi-pi stacking in helical columns.
Article
Chemistry, Multidisciplinary
Dipankar Sahoo, Mihai Peterca, Mohammad R. Imam, Benjamin E. Partridge, Qi Xiao, Virgil Percec
Summary: The primary structure determines the tertiary structure, which in turn determines the function of hierarchical self-organizations. The role of conformational flexibility-rigidity in this process is less understood. Through comparing different molecular structures with varying degrees of conformational flexibility, it was found that more rigid structures provide more stable periodic and quasiperiodic self-organizations, and facilitate the freezing of metastable structures.
Article
Chemistry, Multidisciplinary
Virgil Percec, Ning Huang, Qi Xiao, Benjamin E. Partridge, Dipankar Sahoo, Mohammad R. Imam, Mihai Peterca, Robert Graf, Hans-Wolfgang Spiess, Xiangbing Zeng, Goran Ungar
Summary: Programming complex living and soft matter through primary structure and self-organization is key in designing functions in biological and synthetic nanoscience. Memory effects, such as supramolecular orientational memory (SOM), have been utilized in creating commercial technologies and engineering complex nanoscale soft matter. The discovery of SOM in a non-cubic Frank-Kasper phase suggests the potential expansion of this methodology to other periodic and quasiperiodic nanoarrays in soft and living complex matter.
Article
Chemistry, Multidisciplinary
Qi Xiao, Naomi Rivera-Martinez, Calvin J. Raab, Jessica G. Bermudez, Matthew C. Good, Michael L. Klein, Virgil Percec
Summary: Metal-chelating ligands NTA and TrisNTA bind to His-tagged proteins, which are widely used in cell biology applications to decorate the surface of liposomes. The study found that TrisNTA, a multivalent NTA ligand, displays higher affinity than monovalent NTA when co-assembled with phospholipids and cholesterol in liposomes. To expand the variety of available NTA-conjugated lipids, researchers report a library of stable JD-NTA and JD-TrisNTA, which can co-assemble with liposomes, dendrimersomes, and polymersomes, and exhibit higher activity compared to lipid-NTAs.
