Review
Biochemistry & Molecular Biology
Jose Ferraz-Caetano, Filipe Teixeira, Maria Natalia Dias Soeiro Cordeiro
Summary: This review provides an update on the major works of tunable vanadium-catalyzed epoxidations, focusing on sustainable optimization routes. It discusses the current mechanistic view on vanadium catalysts for small alkenes and allylic alcohols' epoxidation and highlights the key challenges in green process development, emphasizing the value of updated kinetic and mechanistic studies, along with essential computational studies.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Review
Chemistry, Physical
Eliezer Ortiz, Jonathan Shezaf, Yu-Hsiang Chang, Michael J. Krische
Summary: The use of alkynes as vinylmetal pronucleophiles in intermolecular enantioselective metal-catalyzed carbonyl and imine reductive couplings for forming allylic alcohols and amines is explored. Related hydrogen autotransfer processes, where alcohols or amines function as both reductants and carbonyl or imine proelectrophiles, are also discussed, along with their applications in target-oriented synthesis. These processes offer an alternative approach to stoichiometric vinylmetal reagents or Nozaki-Hiyama-Kishi (NHK) reactions in carbonyl and imine alkenylation.
Article
Chemistry, Organic
Lutao Bai, Linqing Wang, Haiyong Zhu, Shiming Pang, Shixin Li, Jiaming Lv, Hailong Zhang, Dongxu Yang
Summary: By developing ProPhenol/Ti(IV) catalysts, a catalytic enantioselective hydroxylative dearomatization of naphthols is achieved using TBHP as a simple oxidative reagent. The side coordinative chain equipped on the C1-position of beta-naphthols plays a crucial role in initiating this asymmetric hydroxylative reaction, likely due to proper cocoordination effects to the titanium center in the catalyst. A reasonable catalytic cycle is proposed, and the catalytic system is applicable to a reasonable range of phenolic compounds of this type, enabling related concise transformations.
Article
Chemistry, Multidisciplinary
Jin Lin, Fang Wang, Jing Tian, Jisheng Zhang, Yong Wang, Wei Sun
Summary: The enantioselective epoxidation of olefin by Mn-II(R,R-PMCP)(OTf)(2), H2O2 and H2SO4 was studied using DFT calculations and experiments. Theoretical results suggest that [Mn-V(O)(R,R-PMCP)(SO4)](+) species acts as the active species for the olefin epoxidation, which is formed with the assistance of H2SO4. Mn-III-persulfate also plays a role in this system but does not directly promote the olefin epoxidation, instead transforming into Mn-V(O) species.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Physical
Mengjun Gong, Yanjun Guo, Daniel Malko, Javier Rubio-Garcia, Jack M. S. Dawson, George J. P. Britovsek, Anthony Kucernak
Summary: Under mild conditions, aldehydes are efficiently converted to epoxides using a heterogeneous Fe-N/C catalyst, which forms the corresponding organic peroxy acid and acylperoxy radicals. Real-time monitoring of oxygen consumption and catalyst potential reveals the formation of peroxy acid and subsequent catalytic epoxidation. The involvement of aldehyde and Fe-N/C catalyst is shown to be the rate determining step for the reaction, and the induction time can be increased by adding a radical scavenger.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Ming Yu Jin, Yali Zhou, Dengmengfei Xiao, Yipeng You, Qianqian Zhen, Guanyu Tao, Peiyuan Yu, Xiangyou Xing
Summary: The mechanistic uniqueness and versatility of borrowing hydrogen catalysis provides an opportunity to investigate the controllability of a cascade reaction, and more importantly, to realize either one or both of chiral recognition and chiral induction simultaneously. In this study, using a robust Ru-catalyst, both kinetic resolution and asymmetric induction were achieved with remarkable levels of efficiency and enantioselectivity, showing the importance of catalyst-substrate pi-pi interactions in realizing stereochemical diversity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Chun-Tai Hung, Chun-Wei Lu, Shi-Han Huang, Yin-Feng Lu, Hsiang-Chi Chou, Cheng-Che Tsai
Summary: This research utilizes chiral sulfinamides as nucleophiles in intramolecular allylic substitution and sequential aerobic oxidation with aza-Michael addition reactions, achieving good yields of chiral isoindolines and high diastereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Aram Rezaei, Huajun Zheng, Shiva Majidian, Saadi Samadi, Ali Ramazani
Summary: This study reports a chiral pseudohomogeneous catalyst that combines the advantages of both homogeneous and heterogeneous catalysts to control the enantioselectivity of the Kharasch-Sosnovsky reaction. The impact of various factors on the allylic oxidation reaction is investigated, and the catalyst is shown to be readily recyclable, making it promising for practical applications.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Xiang Dong, Alexander M. Brown, Audra J. Woodside, Jerome R. Robinson
Summary: Experiments and computations have shown that N-oxides can greatly enhance the performance of a lanthanum aminobisphenolate catalyst in the ring-opening polymerization. It was found that donor electronics control the catalyst activity, while donor sterics control catalyst deactivation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sara Madadi, Serge Kaliaguine
Summary: Ruthenium catalysts supported on various activated carbons were investigated for the epoxidation of limonene using molecular oxygen as the oxidizing agent. Different preparation methods led to catalysts with varying activity and selectivity, with the catalyst prepared by cation exchange showing the best performance. The sol immobilization method resulted in the highest limonene conversion.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Tomoki Niwa, Kousuke Nishibashi, Hitomi Sato, Kiyoshi Ujiie, Kenji Yamashita, Hiromichi Egami, Yoshitaka Hamashima
Summary: In this study, asymmetric fluorofunctionalization of gamma,gamma-disubstituted allylamine derivatives was investigated using a dianionic phase-transfer catalyst, resulting in chiral allylic fluorides and fluorinated dihydrooxazines in a highly enantioselective manner. The influence of the alkene moiety substitution pattern on the reaction was explored, with rate laws indicating the involvement of catalyst ion pair aggregates in the catalytic cycle. Interestingly, the presence or absence of an alkyl substituent at the gamma position of the substrates determined the reaction pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Marcello B. Solomon, Carol Hua, Bun Chan, Tamara L. Church, Seth M. Cohen, Clifford P. Kubiak, Katrina A. Jolliffe, Deanna M. D'Alessandro
Summary: The new metal-organic framework containing a Mn(ii) salen complex undergoes a reversible crystalline-to-amorphous transformation, and is stable to a one-electron reduction at more anodic potentials than the corresponding discrete complex, as supported by experimental studies and computational calculations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Xiang-Hong He, Xue-Ju Fu, Gu Zhan, Nan Zhang, Xiang Li, Hong-Ping Zhu, Cheng Peng, Gu He, Bo Han
Summary: This study describes an organocatalytic asymmetric [3+3] annulation reaction using isatin-derived MBH carbonates and indolin-2-imines. The reaction provides a novel enantioselective approach for the synthesis of multifunctionalized alpha-carboline-spirooxindole hybrids with high yields and stereoselectivities. The synthesized compounds exhibit significant inhibition of proliferation in colorectal cancer cell lines, and the most potent compound activates autophagy and cytoprotective autophagy in HCT116 cells.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Inorganic & Nuclear
Hugo Valdes, Juan M. German-Acacio, Gerard van Koten, David Morales-Morales
Summary: This study explores the synthesis and applications of bimetallic complexes by merging a metallocene and a (cyclopentadienyl/aryl) pincer metal complex, discussing their importance in tuning electronic properties, catalytic reactions, and chiral catalysis. Various approaches to merge metallocene and pincer-metal motifs are explored, showcasing the potential for creating diastereomerically pure derivatives through post-functionalization strategies. The authors aim to inspire further research in this field by highlighting the synthetic, physico-chemical properties, and remarkable catalytic activities of metallocene-based pincer-metal complexes.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Multidisciplinary
Stephany M. Ramos De Dios, Virendra K. Tiwari, Christopher D. McCune, Ranjeet A. Dhokale, David B. Berkowitz
Summary: This review discusses biomacromolecule-assisted screening methods and the discovered chemical reactions. Enzymes, antibodies, and nucleic acids have all been used as sensors to detect product chirality. These biomacromolecule-based screens offer high sensitivity and selectivity, and they have been applied to discover new chemical transformations in synthetic organic chemistry.
Article
Chemistry, Multidisciplinary
Zebediah C. Girvin, Laura F. Cotter, Hyung Yoon, Steven J. Chapman, James M. Mayer, Tehshik P. Yoon, Scott J. Miller
Summary: High selectivity in photochemical reactions can be achieved by controlling the transition state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Sooyun Choi, Melody C. Guo, Gavin M. Coombs, Scott J. Miller
Summary: An atroposelective synthesis method for N-aryl 1,2,4-triazoles was developed. By utilizing a chiral phosphoric acid catalyst, a cyclodehydration reaction achieved asymmetric induction, resulting in atropisomeric N-aryl 1,2,4-triazoles with up to 91:9 enantiomeric ratio. Further crystallization of the isolated heterocycle enhanced the atropisomeric ratio of several analogs to 99:1 or higher. Additionally, a divergent and substrate-dependent reaction pathway leading to a different heterocyclic product was revealed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Marisa C. Kozlowski, Scott J. Miller, Stephane Perreault
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Editorial Material
Chemistry, Inorganic & Nuclear
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, PrashantV. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
INORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Organic
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zoe L. Watson, Isaac J. Knudson, Fred R. Ward, Scott J. Miller, Jamie H. D. Cate, Alanna Schepartz, Ara M. Abramyan
Summary: As genetic code expansion progresses, it is still a challenge to determine the substrates the ribosome can accommodate. This study provides insights into how the E. coli ribosome incorporates non-?-a-amino acids, using high-resolution cryogenic electron microscopy and metadynamics simulations. The findings suggest that reactive monomers prefer a specific conformational space for efficient bonding, which could facilitate the synthesis of non-peptide heterooligomers.
Editorial Material
Chemistry, Organic
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
Article
Multidisciplinary Sciences
Jonas Rein, Soren D. Rozema, Olivia C. Langner, Samson B. Zacate, Melissa A. Hardy, Juno C. Siu, Brandon Q. Mercado, Matthew S. Sigman, Scott J. Miller, Song Lin
Summary: We have developed a catalytic enantioselective method for the oxidative desymmetrization of meso-diols. This method is generally applicable to a broad range of substrates and involves the optimization of a nontraditional catalyst through screening a panel of substrates. By rational modulation of a peptide sequence in the catalyst, a general catalyst with high selectivity and turnover was obtained.
Editorial Material
Chemistry, Physical
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
Editorial Material
Chemistry, Physical
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson
ACS ENERGY LETTERS
(2023)
Editorial Material
Chemistry, Analytical
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
ACS MEASUREMENT SCIENCE AU
(2023)
Editorial Material
Chemistry, Multidisciplinary
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Organic
Susannah E. Huth, Elizabeth A. Stone, Simone Crotti, Scott J. Miller
Summary: During the study of peptide-catalyzed N-oxidations of pyridines, we observed unexpectedly low barriers to atropisomerization under the reaction conditions. Mechanistic studies revealed a hydrogen bond-assisted racemization mechanism inherent to both the starting materials and products. Additionally, a protonation-dependent barrier to rotation was identified for the starting materials alone. Despite this, several substrates could undergo atroposelective N-oxidations via kinetic resolution, with some achieving high enantiomeric ratios (>99:1) after recrystallization.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Benjamin G. Hejna, Jacob M. Ganley, Huiling Shao, Haowen Tian, Jonathan D. Ellefsen, Nicholas J. Fastuca, Kendall N. Houk, Scott J. Miller, Robert R. Knowles
Summary: We present a highly enantioselective radical-based hydroamination of enol esters with sulfonamides using an Ir photocatalyst, Bronsted base, and tetrapeptide thiol. The reaction produces 23 protected β-amino-alcohol products with selectivities up to 97:3 er. Experimental and computational studies reveal that hydrogen bonding, π-π stacking, and London dispersion interactions play important roles in substrate recognition and enantioinduction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jongdoo Lim, Melody Guo, Sooyun Choi, Scott J. Miller, Eric V. Anslyn
Summary: Atropisomeric scaffolds are commonly found in pharmaceuticals and their handedness is crucial for their efficacy and safety. To keep up with the fast workflow of high-throughput screening for drug discovery, a rapid enantiomeric excess (ee) analysis method based on circular dichroism (CD) was developed for N-C axially chiral triazole derivatives. The CD assay showed accurate and efficient ee determination with minimal errors.
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.
