Article
Chemistry, Organic
Jiamin Lu, Ruigang Xu, Haixia Zeng, Guofu Zhong, Meifang Wang, Zhigang Ni, Xiaofei Zeng
Summary: Iridium/Bronsted acid cooperative catalyzed asymmetric allylic substitution reactions at the C5 position of indolines have been reported for the first time. The highly efficient protocol allows rapid access to various C5-allylated products in good to high yields and enantioselectivities with wide functional group tolerance. The transformations not only enable the formation of C5-allylindoline derivatives, but also the synthesis of C5-allylindole analogues in good yields and excellent stereoselectivities via an allylation/oxidation reaction sequence.
Article
Chemistry, Organic
Yunpeng Chu, Fang Hu, Peng Feng, Xin-Ping Hui
Summary: The first N-heterocyclic carbene-catalyzed enantioselective dearomatizing annulation of benzoxazoles with alpha,beta-unsaturated aldehydes has been achieved, resulting in moderate to good yields and moderate to excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Multidisciplinary
Kun-Quan Chen, He Sheng, Qiang Liu, Pan-Lin Shao, Xiang-Yu Chen
Summary: In recent years, NHC-catalyzed radical reactions have been gaining attention for their potential to create new activation modes previously inaccessible. Further research and understanding of this emerging area is warranted to explore its synthetic techniques and advantages.
SCIENCE CHINA-CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Tingting Li, Zhichao Jin, Yonggui Robin Chi
Summary: This review discusses N-heterocyclic carbene-catalyzed reactions for the formation of aromatic compounds, categorizing them into 4 types based on activation modes. The achievements, challenges, and future research directions in NHC-catalyzed arene construction processes are summarized. The outlook is based on the authors' opinions and knowledge on the trends of NHC organocatalysis development.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
En Li, Kai Tang, Zhuhui Ren, Xiaoyun Liao, Qianchen Liu, Yong Huang, Jiean Chen
Summary: The successful enantioselective beta-alkylation of homoenolates using C-sp3 electrophiles through an S(N)2 strategy is reported. The method shows a broad scope and delivers good yields and excellent enantioselectivities (up to 99% ee). It enables the installation of drug-like structural motifs and presents a concise synthetic route to chiral pyrroloindoline-type skeletons. Preliminary mechanistic studies support a direct S(N)2 mechanism.
Article
Chemistry, Organic
Min Zhang, Xinghua Wang, Tingting Yang, Yan Qiao, Donghui Wei
Summary: Identifying the special role of N-heterocyclic carbene (NHC) in organocatalysis remains a major challenge. The study proposed a theoretical model for NHC-catalyzed decarboxylation reactions and found that C-H⋯O hydrogen bond interactions significantly contribute to controlling stereoselectivity in these reactions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Physical
Guangjin Zhen, Kai Jiang, Biaolin Yin
Summary: Dearomative reactions enable the concise assembly of highly functionalized three-dimensional molecules by disrupting the aromaticity of starting materials. N-heterocyclic carbenes (NHCs) have emerged as powerful catalysts for dearomatization reactions, allowing for the construction of natural product and drug skeletons. This overview summarizes the progress in NHC-catalyzed dearomative reactions, classifying the reactions by modes and categories of intermediates and providing representative mechanisms.
Review
Chemistry, Multidisciplinary
Lei Dai, Song Ye
Summary: N-heterocyclic carbene (NHC)-catalyzed reactions involving two-electron and radical pathways have been well-established, with the former more developed than the latter in terms of reaction types and enantioselectivity. In the past decade, several elegant NHC-catalyzed radical reactions have been developed, including oxidation of aldehydes, reductive coupling reactions, and reactions via radical homoenolates.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Yiu-Wai Yeung, Chun-Ming Chan, Yu-Ting Chen, Marco Chan, Mingyu Luo, Xin Gao, Bingnan Du, Wing-Yiu Yu
Summary: We have developed a Cu-catalyzed cross-electrophilic coupling reaction for the synthesis of alpha-amino acid derivatives using alpha diazoesters and O-benzoyl hydroxylamines. Cu(OAc)2 is used as the catalyst and polymethylhydrosilane (PMHS) as the hydride reagent. The reaction demonstrates excellent functional group compatibilities. The formation of a Cuacetoacetate complex was confirmed by ESI-MS analysis, and radical trap experiments suggest the involvement of nitrogen-centered radicals as intermediates. This strategy provides a simple and cost-effective approach for the synthesis of alpha-amino acid derivatives.
Article
Chemistry, Multidisciplinary
Anthony F. Tierno, Jennifer C. Walters, Andres Vazquez-Lopez, Xiao Xiao, Sarah E. Wengryniuk
Summary: This study utilizes N-HVI reagents as heterocyclic group transfer reagents to provide a broad scope of N-alkyl(heteroaryl)onium salts via aminolactonization of alkenoic acids, showcasing a novel method for their synthesis.
Article
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Peng-Shuai Xu, Xin-Hang Jin, Chuan Xie, Qi-Chun Yang, Xiang Zhang, Jun-Long Li
Summary: In this study, a cross-coupling reaction of aldehydes with unactivated alkyl halides was developed through N-heterocyclic carbene catalysis, enabling the synthesis of various ketones. This method offers the advantages of mild reaction conditions and readily available starting materials, and has been successfully applied in the functionalization of pharmaceutical derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Peng-Shuai Xu, Xin-Hang Jin, Chuan Xie, Qi-Chun Yang, Xiang Zhang, Jun-Long Li
Summary: Catalytic cross-coupling reaction of aldehydes with unactivated alkyl halides was achieved via N-heterocyclic carbene catalysis. This method enables rapid synthesis of various ketones from readily available starting materials under mild conditions. The organocatalytic system was successfully applied in the late-stage functionalization of pharmaceutical derivatives. Mechanistic investigations suggest a closed-shell nucleophilic substitution mechanism for this reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Kosuke Yasui, Miharu Kamitani, Hayato Fujimoto, Mamoru Tobisu
Summary: This study reports on the N-heterocyclic carbene (NHC)-catalyzed Truce-Smiles rearrangement of aniline derivatives, where an unactivated C(aryl)-N bond is cleaved to form a new C(aryl)-C bond. The key to the success of this reaction lies in the utilization of highly nucleophilic NFIC, which enables the formation of a highly nucleophilic ylide intermediate generated from an alpha,beta-unsaturated amide.
Article
Chemistry, Organic
Killari Satyam, Jakkula Ramarao, Surisetti Suresh
Summary: The NHC-catalyzed intramolecular benzoin condensation-oxidation allows for the expedient synthesis of diverse cyclic 1,2-diketones incorporated in dibenzo-fused seven-membered heterocycles in good to excellent yields under ambient conditions. The transformation appears to proceed through the benzoin intermediate followed by aerobic oxidation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Qi Xu, Huan Zhang, Fang-Bei Ge, Xiao-Mei Wang, Peng Zhang, Chuan-Jun Lu, Ren-Rong Liu
Summary: In this study, we demonstrate that copper(I) catalysis using a bis(phosphine) dioxide ligand can efficiently catalyze the desymmetric C-H arylation of prochiral bipyrroles with excellent enantioselectivities. More than 50 nitrogen-nitrogen atropisomers were achieved in good to excellent yields. The mild reaction conditions and good functional group compatibility on arenes and diaryliodonium salts make this method highly versatile.
Article
Chemistry, Organic
Samantha L. Goldschmid, Eva Bednarova, Logan R. Beck, Katherine Xie, Nicholas E. S. Tay, Benjamin D. Ravetz, Jun Li, Candice L. Joe, Tomislav Rovis
Article
Multidisciplinary Sciences
Hengrui Liu, Sho Iketani, Arie Zask, Nisha Khanizeman, Eva Bednarova, Farhad Forouhar, Brandon Fowler, Seo Jung Hong, Hiroshi Mohri, Manoj S. Nair, Yaoxing Huang, Nicholas E. S. Tay, Sumin Lee, Charles Karan, Samuel J. Resnick, Colette Quinn, Wenjing Li, Henry Shion, Xin Xia, Jacob D. Daniels, Michelle Bartolo-Cruz, Marcelo Farina, Presha Rajbhandari, Christopher Jurtschenko, Matthew A. Lauber, Thomas McDonald, Michael E. Stokes, Brett L. Hurst, Tomislav Rovis, Alejandro Chavez, David D. Ho, Brent R. Stockwell
Summary: The authors have described small molecule inhibitors of the SARS-CoV-2 3CL protease for potential treatment of COVID-19. These inhibitors have shown promising antiviral activity and could serve as valuable tools in controlling the ongoing pandemic.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Finn Burg, Tomislav Rovis
Summary: In this study, a modular strategy for diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- and N-nucleophiles with readily available 3-substituted 1,4,2-dioxazolones has been reported. The use of hexafluoroisopropanol as a non-nucleophilic solvent allows for the use of diverse nucleophiles and greatly expands the scope of the transformation.
Article
Chemistry, Multidisciplinary
Nicholas Eng Soon Tay, Keun Ah Ryu, John L. Weber, Aleksandra K. Olow, David C. Cabanero, David R. Reichman, Rob C. Oslund, Olugbeminiyi O. Fadeyi, Tomislav Rovis
Summary: State-of-the-art photoactivation strategies in chemical biology provide control and visualization of biological processes. However, using high-energy light for sensitization can lead to background activation of probes. This study presents the development of targeted aryl azide activation via deep red-light photoredox catalysis and its application in photocatalysed proximity labelling.
Article
Chemistry, Multidisciplinary
Christopher W. Lamartina, Cassandra A. Chartier, Sumin Lee, Neel H. Shah, Tomislav Rovis
Summary: Here, a modular peptide ligation methodology is reported, which uses Rh(III) catalysis to couple dioxazolones, arylboronic acids, and acrylamides to construct amide bonds in a diastereoselective manner under mild conditions. The method shows excellent functional group tolerance and a large substrate scope, allowing for the construction of unnatural amino acid residues. This methodology is demonstrated in the synthesis of diastereomeric proteasome inhibitor analogs and the ligation of oligopeptides to construct a polypeptide with an unnatural residue.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Noah Wagner-Carlberg, Tomislav Rovis
Summary: In this study, a general method for the intermolecular anti-Markovnikov hydroamidation of unactivated alkenes was developed, utilizing Rh(III) catalysis in conjunction with dioxazolone amidating reagents and isopropanol as an environmentally friendly hydride source. The reaction showed good tolerance towards various functional groups and efficiently converted different types of alkenes into their corresponding linear amides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xiao Zhang, Yangyang Shen, Tomislav Rovis
Summary: We reported a mild, catalytic approach for the demethylation of trialkylamines using photoinduced nickel catalysis. C(sp2)-bromides serve as hydrogen-atom transfer reagents in this process, achieving direct demethylation with wide functional group compatibility. Mechanistic investigations reveal the involvement of C(sp2) radicals generated via photoinduced Ni-C(sp2) bond homolysis in the hydrogen atom abstraction from trialkylamines. Our approach shows excellent site selectivity in the demethylation reactions of benzyl-substituted amines, complementing the selectivity of classical approaches.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Samantha L. Goldschmid, Nicholas Eng Soon Tay, Candice L. Joe, Brendan C. Lainhart, Trevor C. Sherwood, Eric M. Simmons, Melda Sezen-Edmonds, Tomislav Rovis
Summary: Aryl amination plays a crucial role in medicinal, process, and materials chemistry. Blue-light-driven metallaphotoredox catalysis is a valuable tool for C-N cross-coupling, but its limited penetration through reaction media and the formation of unwanted side-products pose challenges for industrial scalability. Using low-energy light, such as deep red or near-infrared, can enhance penetration and suppress unwanted reactions, leading to an enhanced scope of aryl bromides and amine-based nucleophiles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sean M. M. Treacy, Daniel R. R. Vaz, Syed Noman, Cedric Tard, Tomislav Rovis
Summary: gamma-Lactams, which are commonly found in small-molecule pharmaceuticals, can be used as precursors for highly substituted pyrrolidines. Previously, redox approaches to gamma-Lactam synthesis required additional electron withdrawing functionality and N-aryl substitution to promote electrophilicity and prevent undesired reactions. However, a new strategy using alpha-bromo imides and alpha-olefins enables the synthesis of monosubstituted protected gamma-Lactams in a formal [3 + 2] fashion, offering opportunities for further derivatization.
Article
Chemistry, Multidisciplinary
Xiye Wang, Boyuan Zhang, Brandon Fowler, Latha Venkataraman, Tomislav Rovis
Summary: The electric field acceleration of alkyl hydroperoxide activation to acylate amines in the scanning tunneling microscope-based break-junction is reported. It was found that alkyl hydroperoxide mixtures, generated from hydrocarbon autoxidation in air, are competent reagents for the functionalization of gold surfaces. Intermolecular coupling on the surface in the presence of amines was observed, yielding normal alkylamides. This novel mode of alkyl hydroperoxide activation is found to be responsive to the magnitude of the bias in the break junction, indicating an electric field influence on this novel reactivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Ryan W. Clarke, Tobias Sandmeier, Kevin A. Franklin, Dominik Reich, Xiao Zhang, Nayan Vengallur, Tarak K. Patra, Robert J. Tannenbaum, Sabin Adhikari, Sanat K. Kumar, Tomislav Rovis, Eugene Y. -X. Chen
Summary: The global plastics problem has a significant impact on the environment, energy, and climate. Various innovative strategies have been proposed to address these issues and achieve a circular economy. However, the challenge of reusing mixed-plastics waste remains, as there is currently no effective closed-loop solution.
Article
Chemistry, Physical
David C. Cabanero, Jennifer A. Nguyen, Catherine S. J. Cazin, Steven P. Nolan, Tomislav Rovis
Summary: A system has been developed that uses deep red to near-infrared light to activate a latent ruthenium olefin metathesis catalyst. This is achieved by using an osmium(II) photocatalyst that is excited to its triplet state and a latent solvent-coordinated, cationic precatalyst that undergoes excited-state single-electron reduction. The system demonstrates excellent spatiotemporal control under light irradiation and shows improved light penetration through barriers.
Article
Chemistry, Organic
Logan R. Beck, Katherine A. Xie, Samantha L. Goldschmid, Stavros K. Kariofillis, Candice L. Joe, Trevor C. Sherwood, Melda Sezen-Edmonds, Tomislav Rovis
Summary: Photoredox catalysis has transformed synthetic chemistry and researchers have been exploring the use of low-energy deep red (DR) or near-infrared (NIR) light to overcome the limitations of high-energy blue/ultraviolet light. This graphical review summarizes the photophysical principles relevant to photoredox catalysis and reviews applications that benefit from low-energy irradiation, including large-scale batch reactions, photodynamic therapy, biological labeling, and multi-photon excitation.
Article
Chemistry, Multidisciplinary
Julia R. Dorsheimer, Tomislav Rovis
Summary: Stable isotopes have significant applications in chemistry and drug discovery. This study presents a method using a simple benzophenone imine as the N-15 source to access N-15-labeled primary amines through late-stage isotopic exchange.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jennifer A. Nguyen, David C. Cabanero, Tomislav Rovis
Summary: A system for electrochemically controlling ruthenium-catalyzed olefin metathesis has been developed. This system, catalyzed by a commercially-available bis-NHC Ru complex, exhibits a wide substrate scope with short reaction times, and achieves excellent temporal control over metathesis using only electricity as a stimulus.
Article
Chemistry, Multidisciplinary
Alexander M. Prophet, Kritanjan Polley, Gary J. Van Berkel, David T. Limmer, Kevin R. Wilson
Summary: The oxidation kinetics of iodide by ozone at the air-water interface is studied in single microdroplets. Molecular simulations and kinetic modeling are used to understand the underlying multiphase mechanism.
Article
Chemistry, Multidisciplinary
Rong Zhang, Jiajing Lan, Fei Wang, Shumei Chen, Jian Zhang
Summary: By utilizing 1,1'-ferrocene dicarboxylic acid as a chelating and surface protection ligand, we have synthesized multi-nuclear indium oxide clusters with varying nuclear sizes, including heptanuclear and thirteen-nuclear clusters. These clusters possess labile coordination sites, allowing for structural modification and self-assembly, resulting in the formation of various cluster structures.
Article
Chemistry, Multidisciplinary
Hui Wang, Hui Liu, Mingsen Wang, Jiaheng Hou, Yongjun Li, Yuancheng Wang, Yingjie Zhao
Summary: Two supramolecular complexes were prepared using CBs and M1, and their single-crystal structures were analyzed by SCXRD. The unexpected 1:2 self-assembly structure between M1 and CB[8] was discovered for the first time. These complexes exhibit unique photophysical properties and provide valuable information about the structure and photophysical properties of supramolecular complexes.
Article
Chemistry, Multidisciplinary
Chang-Hee Lee, Sookil Park, Sanggil Kim, Ji Young Hyun, Hyun Soo Lee, Injae Shin
Summary: The epidermal growth factor receptor (EGFR) is a cell-surface glycoprotein involved in cell proliferation and tumor development. This study used a fluorescently labeled EGFR to investigate its time-dependent endocytosis in live cells and found that appended glycans affect EGFR internalization. Additionally, the study detected sialic acid residues attached to EGFR on the live cell surface using FRET-based imaging. This research provides valuable insights into the cellular functions of EGFR.
Article
Chemistry, Multidisciplinary
Subhankar Sahu, Lokesh Kumar, Sumita Das, Dipti Gupta, Ruchi Anand
Summary: This study proposes a strategy that combines organic electronics with biosensor scaffolds to create a compact device for monitoring environmental aromatic pollution. By coupling biosensing protein MopR with an organic electrochemical transistor (OECT), a sensor module capable of efficient detection of phenol was designed. Exclusive phenol detection with minimal loss of sensitivity could be achieved in complex pollutant mixtures and real environmental samples.
Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Multidisciplinary
Yueci Wu, Lu-Lu Sun, Hai-Hao Han, Xiao-Peng He, Weiguo Cao, Tony D. James
Summary: Drug-induced liver injury (DILI) is a common cause of acute liver failure in the USA and Europe, but most cases can be recovered or prevented by discontinuing the offending drug. Recent research has found that peroxynitrite (ONOO-) can be used as a potential indicator for early diagnosis of DILI, and there is an urgent need to establish a method to detect and track peroxynitrite in DILI cases. In this study, a FRET-based nano fluorescent probe CD-N-I was developed, which showed high selectivity and sensitivity in detecting peroxynitrite. The probe successfully detected exogenous peroxynitrite in live cells and endogenous peroxynitrite in APAP-induced liver injury of HepG2 cells.
Article
Chemistry, Multidisciplinary
Dmitry L. Lipilin, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman
Summary: This article describes a direct photocatalytic method for the thiolation of unprotected acids, which was previously challenging. By using a thionocarbonate reagent with an N-O bond, the efficient conversion of carboxylic acids to thiols is achieved.
Article
Chemistry, Multidisciplinary
Jason Malenfant, Lucille Kuster, Yohann Gagne, Kouassi Signo, Maxime Denis, Sylvain Canesi, Mathieu Frenette
Summary: Raman microscopy can reveal compound-specific vibrational fingerprints without sample preparation. The combination of efficient theoretical calculations and a user-friendly software can accurately predict peak positions and provide match scores to assist with structure determination.
Article
Chemistry, Multidisciplinary
Jayoh A. Hernandez, Paul S. Micus, Sean Alec Lois Sunga, Luca Mazzei, Stefano Ciurli, Gabriele Meloni
Summary: Essential trace metals play crucial roles in the survival and virulence of bacterial pathogens. Helicobacter pylori requires nickel for colonization and persistence in the stomach, and NixA is an essential nickel transporter in this process. This study characterizes the selectivity and electrogenic nature of NixA-mediated nickel transport.
Article
Chemistry, Multidisciplinary
Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.
Article
Chemistry, Multidisciplinary
Jacqueline R. Santhouse, Jeremy M. G. Leung, Lillian T. Chong, W. Seth Horne
Summary: By studying the folding kinetics and mechanism of the BdpA sequence, researchers found that altering the backbone connectivity can affect protein folding. This suggests that protein mimetic chains have a significant degree of plasticity in transitioning between unfolded and folded states.
Article
Chemistry, Multidisciplinary
Divanshu Gupta, Ralf Einholz, Holger F. Bettinger
Summary: This study presents the first direct spectroscopic evidence of a cyclic seven-membered iminoborane. Compared to linear amino-iminoboranes, this cyclic iminoborane exhibits weakened bond strength and lower Lewis acidity value. The study suggests that the reduced ring strain of cyclic iminoborane prevents nitrogen fixation but allows facile (2 + 2) cycloaddition reaction with C2H4.
Article
Chemistry, Multidisciplinary
Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas
Summary: This study reveals the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI) using a synergistic approach that combines 3D ED, ssNMR, and DFT techniques. By overcoming these challenges, this methodology opens up new avenues for material characterization, driving exciting advancements in the field.
