Article
Chemistry, Multidisciplinary
Austin S. Miller, Erik J. Alexanian
Summary: The late-stage introduction of diverse heterocycles onto complex small molecules enables efficient access to new medicinally relevant compounds. Here, we report a system that enables direct C-H heteroarylation using a stable, commercially available O-alkenylhydroxamate with heterocyclic sulfone partners. The C-H heteroarylation proceeds efficiently with a range of aliphatic substrates and common heterocycles, and is a rare example of heteroarylation of strong C-H bonds. Importantly, the present approach is amenable to late-stage functionalization as the substrate is the limiting reagent in all cases.
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, Organic
Yang Hong, Meng-Yuan Dong, Dong-Sheng Li, Hong-Ping Deng
Summary: This article reports a general and mild strategy for three-component carboarylation of unactivated alkenes with protic C(sp3)-H feedstocks via photoredox catalysis. The catalytic system is compatible with a broad range of unactivated alkenes, cyano-substituted arenes, and diverse protic C(sp3)-H feedstocks. The synthetic value of this method was demonstrated by late-stage functionalization of complex molecules and the synthesis of antiallergies including pheniramine, chlorpheniramine, and brompheniramine.
Article
Chemistry, Multidisciplinary
Zi-Tong Pan, Xu-Kuan Qi, Qian Xiao, Xi-Wen Liang, Jian-Ji Zhong, Jing-Xin Jian, Qing-Xiao Tong
Summary: In this study, we have demonstrated a regulable cross-coupling reaction using alcohols as alkylating reagents to functionalize benzothiazoles. We obtained two types of cross-coupling products with high isolated yields, opening up a broad research prospect for expanding alcohols as alkylating reagents.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Pengzhi Wang, Anna V. Bay, Emelia J. Farnam, Karl A. Scheidt
Summary: A mild photocatalyzed method for the a-alkylation of esters via formation of an a-radical is reported. Cesium enolates of esters were generated in situ using Cs2CO3 as a base. Photocatalyzed oxidation at the a-carbon of these enolates produced an a-radical, which was then added into activated alkenes. This is the first example accessing the a-carbon radical of esters in photoredox-catalyzed transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Prahallad Meher, Satya Prakash Panda, Sanat Kumar Mahapatra, Karan Ramdas Thombare, Lisa Roy, Sandip Murarka
Summary: We report a photoredox system that can form a self-assembled complex and activate diaryliodonium reagents for arylation of heterocycles under mild conditions.
Article
Chemistry, Organic
Yan-Shun Zhang, Yin Wei, Min Shi
Summary: This study presents a sequential dual catalytic transformation for the rapid synthesis of polysubstituted caged oxa-bishomocubane products. The method is simple and utilizes readily available starting materials, providing good step-economy.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Letter
Chemistry, Organic
Yumo Zhao, Yi Wan, Qiyang Yuan, Jinlian Wei, Yongqiang Zhang
Summary: A visible-light-induced photocatalytic C-Si formation strategy was developed using Martin's spirosilane-derived pentacoordinate silylsilicates as silyl radical precursors. The strategy exhibited efficient hydrosilylation of a wide range of alkenes and alkynes, as well as C-H silylation of heteroarenes. Notably, Martin's spirosilane was stable and could be easily recovered. Moreover, the reaction performed well using water as the solvent or low-energy green LEDs as an alternative energy source.
Article
Chemistry, Multidisciplinary
Matthias Krumb, Lisa Marie Kammer, Shorouk O. Badir, Maria Jesus Cabrera-Afonso, Victoria E. Wu, Minxue Huang, Adam Csakai, Lisa A. Marcaurelle, Gary A. Molander
Summary: DEL technology is a time- and cost-efficient method for identifying therapeutic candidates in the pharmaceutical industry, but there is still a lack of DNA-compatible reactions that can use building blocks from readily available substructures under mild, dilute, and aqueous conditions for further library diversification.
Article
Chemistry, Organic
David T. Mooney, Peter R. Moore, Ai-Lan Lee
Summary: A new method has been developed for the direct C-H carboxyamidation of purines, allowing for the installation of primary, secondary, and tertiary amides. This metal-free and affordable approach is operationally simple and suitable for late-stage functionalizations of biologically important molecules.
Article
Chemistry, Multidisciplinary
Zhoumei Tan, Xinrui He, Kun Xu, Chengchu Zeng
Summary: This study reports a new electrophotocatalytic strategy to access alkyl radicals from strong C(sp(3))-H bonds, which can be applied in Minisci alkylation reactions without the use of chemical oxidants. This method realizes the direct Minisci alkylation reaction from abundant unactivated alkanes with high atom economy.
Article
Chemistry, Organic
Wenwen Cui, Xufeng Li, Guoju Guo, Xiuyan Song, Jian Lv, Daoshan Yang
Summary: In this study, a copper-catalyzed blue-light-induced free radical ring-opening reaction of sulfonium salts with dichalcogenides was developed. The method utilizes an inexpensive copper catalyst and has a broad substrate scope, allowing for the high-yield synthesis of alkyl chalcogenides. This reaction presents a novel ring-opening model for sulfonium salts, breaking the limitation of only nucleophilic ring-opening reactions to form C-heteroatom and C-C bonds.
Review
Chemistry, Applied
Alessandro Palmieri, Marino Petrini
Summary: The limited nucleophilic character and bidentate nature of unactivated nitroalkane anions make alkylation and allylation procedures troublesome. This review summarizes the most rewarding approaches, mainly based on metal-catalyzed processes involving purely ionic or mixed ionic-radical intermediates, that have been devised to overcome this limitation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Pinku Prasad Mondal, Amit Pal, Subham Das, Sariga Mangalamundackal Vijayan, Anagha Veluthanath Nair, Shubham Ojha, Basudev Sahoo
Summary: We present a metal-free visible-light-mediated C(sp(2))-H alkylation of N-heteroarenes with dihydroquinazolines derived from aliphatic ketones under oxidative conditions. This strategy enables the construction of C-C bonds through a Minisci-type reaction, activating the native C-H bond of the N-heteroarene and an α-C-C bond of a readily available ketone. The versatility of this mild method allows for the use of various N-heteroarenes and ketones, with tolerance towards a broad range of functional groups.
Article
Chemistry, Organic
Debabrata Das, Krishna Gopal Ghosh, Sumit Garai, Chandu Palasetty, Sureshkumar Devarajulu
Summary: A visible-light-driven organophotocatalyzed multi-component approach is developed for carbothiolation of activated alkenes under environmentally friendly and redox-neutral conditions. The protocol involves C(sp(3))-H functionalization followed by electrophilic alkyl/arylthiolation, offering a complete transition-metal and peroxide-free process. The method demonstrates excellent functional group tolerance and chemoselectivity, and is made more sustainable and energy efficient by utilizing natural sunlight and an inexpensive and easy-to-prepare pyrylium salt as an organo-photocatalyst.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Terry McCallum, Louis Barriault
JOURNAL OF ORGANIC CHEMISTRY
(2015)
Article
Chemistry, Organic
Sherif J. Kaldas, Alexandre Cannillo, Terry McCallum, Louis Barriault
Article
Chemistry, Organic
Huy Tran, Terry McCallum, Mathieu Morin, Louis Barriault
Article
Chemistry, Organic
Terry McCallum, Laurie-Anne Jouanno, Alexandre Cannillo, Louis Barriault
Article
Chemistry, Physical
C. D. McTiernan, M. Morin, T. McCallum, J. C. Scaiano, L. Barriault
CATALYSIS SCIENCE & TECHNOLOGY
(2016)
Article
Chemistry, Multidisciplinary
T. McCallum, S. P. Pitre, M. Morin, J. C. Scaiano, L. Barriault
Article
Chemistry, Organic
M. Zidan, T. McCallum, L. Thai-Savard, L. Barriault
ORGANIC CHEMISTRY FRONTIERS
(2017)
Article
Chemistry, Multidisciplinary
Guillaume Revol, Terry McCallum, Mathieu Morin, Fabien Gagosz, Louis Barriault
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2013)
Article
Chemistry, Organic
Terry McCallum, Ekaterina Slavko, Mathieu Morin, Louis Barriault
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2015)
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.