News Item
Chemistry, Multidisciplinary
Karoline T. Neumann, Troels Skrydstrup
Summary: The direct carbon isotope exchange reaction on alpha-amino acids is highly desirable as it allows for the direct formation of C-11, C-13, and C-14-labelled alpha-amino acids. This new method involving aldehyde-catalysed carboxylate exchange with isotopically labelled *CO2 bypasses the need for multiple synthetic steps and harsh conditions.
Review
Chemistry, Multidisciplinary
David M. Kitcatt, Simon Nicolle, Ai-Lan Lee
Summary: This review summarizes the recent progress on using carboxylic acids directly as convenient radical precursors for the formation of carbon-carbon bonds.
CHEMICAL SOCIETY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Alexandre Labiche, Augustin Malandain, Maxime Molins, Frederic Taran, Davide Audisio
Summary: In contrast to stable and natural abundant carbon-12, the synthesis of organic molecules with carbon (radio) isotopes requires careful planning and optimization due to the challenges of radiochemical requirements. Recently, carbon isotope exchange technologies have emerged as effective methods for late-stage labeling, utilizing primary radiolabeled building blocks and various activation processes. This review provides a brief overview of these technologies and their potential impact on radiosynthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sean W. Reilly, Yu-hong Lam, Sumei Ren, Neil A. Strotman
Summary: This study presents a facile one-pot strategy for (CN)-C-13 and (CN)-C-14 exchange with aryl, heteroaryl, and alkenyl nitriles using a Ni phosphine catalyst and BPh3. The method employs labeled Zn(CN)(2) to facilitate enrichment, eliminating de novo synthesis for precursor development. Preliminary experimental and computational studies suggest Lewis acid BPh3 is not critical for the oxidative addition step but helps facilitate CN exchange on Ni.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Elisabetta Rosadoni, Elena Bombonato, Antonio Del Vecchio, Sara Guariento, Paolo Ronchi, Fabio Bellina
Summary: This note discusses the application of a Minisci-type reaction for the direct alkylation of azoles with carboxylic acids as radical precursors. Different reaction conditions were investigated to achieve high yield of the desired products, focusing on acid strength and solvent screening. Moreover, the reactivity of imidazoles with various carboxylic acids was investigated, showing good yield for most cases. The study reveals the potential of this approach for late-stage functionalization in drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Masanori Shigeno, Kazuya Hanasaka, Itsuki Tohara, Koki Izumi, Hiroyuki Yamakoshi, Eunsang Kwon, Kanako Nozawa-Kumada, Yoshinori Kondo
Summary: CO2 fixation into electron-deficient aromatic C-H bonds using a combination of Bronsted bases LiO-t-Bu and LiO-t-Am/CsF/18-crown-6 (t-Am = CEtMe2) under a CO2 atmosphere leads to the formation of various polyfunctionalized aromatic carboxylic acids.
Article
Chemistry, Multidisciplinary
Ke Zhang, Bai-Hao Ren, Xiao-Fei Liu, Lin-Lin Wang, Min Zhang, Wei-Min Ren, Xiao-Bing Lu, Wen-Zhen Zhang
Summary: This paper reports a highly selective and direct electroreductive ring-opening carboxylation of epoxides with CO2 in an undivided cell, showing broad substrate scopes within styrene oxides and providing a practical and scalable access to important synthetic intermediate β-hydroxy acids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Zhengning Fan, Shenhao Chen, Song Zou, Chanjuan Xi
Summary: The carboxylation reaction of allylic alcohols with carbon dioxide is achieved using photoredox/nickel dual catalysis, resulting in exclusively linear acids with good Z/E stereoselectivity. The use of Hantzsch ester as a reductant instead of stoichiometric metallic reductants allows the reaction to be carried out at room temperature with a blue LED light source. Mechanistic studies indicate that the presence of water in the catalytic system is crucial for the success of the reaction, which is likely to proceed through the oxidative addition of the in situ formed allylic hydrogen carbonate.
Article
Chemistry, Physical
Kohei Takahashi, Yuji Sakurazawa, Asaki Iwai, Nobuharu Iwasawa
Summary: The catalytic 1,1-dicarboxylation of ethylene with CO2 to form a methylmalonate salt was achieved using a Ni/Ir dual-catalyst system under photoirradiation conditions. Mechanistic investigations revealed the involvement of photoenergy in both the reduction of the Ni(II) complex and the transformation of the nickelalactone to the methylmalonate complex.
Review
Chemistry, Multidisciplinary
Jacob Davies, Julien R. Lyonnet, Dmitry P. Zimin, Ruben Martin
Summary: While there has been considerable interest in the synthetic potential of carbon dioxide as a renewable C1 chemical feedstock in the past decade, little effort has been made to improve the robustness and applicability of established carboxylation methodologies. This lack of advancement hinders their uptake in the industrial sector and poses a challenge for their wider adoption.
Article
Chemistry, Multidisciplinary
Xuyong Wang, Wen-Yan Tong, Bing Huang, Si Cao, Yunlong Li, Jingchao Jiao, Hang Huang, Qiu Yi, Shuanglin Qu, Xi Wang
Summary: A general protocol for the synthesis of 1,4-dicarbonyl Z-alkenes from alkynes using alpha-diazosulfonium triflate and water has been reported, showing excellent Z-selectivity and complete regioselectivity. The resulting compounds can be smoothly converted to various heteroaromatic scaffolds. Mechanistic studies suggest the formation of a free carbyne radical intermediate and the crucial role of KH2PO4 in enhancing yield and selectivity, providing a new direction for radical coupling reactions of diazo compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Cheng Y. Zhang, Yan J. Chen, Ya Y. Wang, Xin H. Peng
Summary: A base medium system generated from the reaction between Cs2CO3 and t-BuOK is effective for the carboxylation of imidazoles and other heterocyclic arenes with CO2. Density functional theory calculations reveal that the formation of t-BuOCs is an endothermic process. The presence of t-BuOCs facilitates the deprotonation of substrates and the electrophilic insertion of CO2.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Sanjeev Kumar, Ajay K. Singh
Summary: In the past few decades, various strategies have been developed for the synthesis of cross-electrophile coupling products through the activation of C(sp(3))-O bonds. However, the use of expensive catalysts, stoichiometric oxidants or reductants, and the low gas-liquid reaction surface-to-volume ratio pose significant challenges in this field.
Article
Horticulture
Juan Carlos Suarez, Jose Alexander Anzola, Amara Tatiana Contreras, Dina Luz Salas, Jose Ivan Vanegas, Milan O. Urban, Stephen E. Beebe, Idupulapati M. Rao
Summary: The objective of this study was to determine the photosynthetic and grain yield responses of two common bean lines to intercropping with maize under different fertilizer applications in the Colombian Amazon region. The results showed that both bean lines had improved photosynthetic efficiency and yield when intercropped with maize and using organic fertilizer, with significant effects during the pod filling growth stage. This study suggests that small farmers in the Amazon region can benefit from intercropping beans with maize and using organic fertilizer.
SCIENTIA HORTICULTURAE
(2022)
Article
Chemistry, Organic
Lingfei Hu, Han Gao, Yanlei Hu, Xiangying Lv, Yan-Bo Wu, Gang Lu
Summary: The mechanism and origins of regio- and stereoselectivities of Cu-catalyzed alkyne difunctionalization with CO2 and trialkyl boranes were computationally investigated. The results show that vicinal addition is disfavored due to the inertness of the alkyl copper intermediate. Favored geminal addition proceeds through a cationic Cu-mediated migration pathway. Energy decomposition analysis reveals that σ)(π Pauli repulsion is the dominant factor controlling stereoselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Juntao Ye, Zhihao Shi, Theresa Sperger, Yoshifumi Yasukawa, Cian Kingston, Franziska Schoenebeck, Mark Lautens
Article
Chemistry, Organic
Cian Kingston, Patrick J. Guiry
JOURNAL OF ORGANIC CHEMISTRY
(2017)
Article
Multidisciplinary Sciences
Kyle W. Knouse, Justine N. deGruyter, Michael A. Schmidt, Bin Zheng, Julien C. Vantourout, Cian Kingston, Stephen E. Mercer, Ivar M. Mcdonald, Richard E. Olson, Ye Zhu, Chao Hang, Jason Zhu, Changxia Yuan, Qinggang Wang, Peter Park, Martin D. Eastgate, Phil S. Baran
Article
Chemistry, Organic
Cian Kingston, Jinju James, Patrick J. Guiry
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Shengyang Ni, Natalia M. Padial, Cian Kingston, Julien C. Vantourout, Daniel C. Schmitt, Jacob T. Edwards, Monika M. Kruszyk, Rohan R. Merchant, Pavel K. Mykhailiuk, Brittany B. Sanchez, Shouliang Yang, Matthew A. Perry, Gary M. Gallego, James J. Mousseau, Michael R. Collins, Robert J. Cherney, Pavlo S. Lebed, Jason S. Chen, Tian Qin, Phil S. Baran
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Review
Chemistry, Multidisciplinary
Cian Kingston, Maximilian D. Palkowitz, Yusuke Takahira, Julien C. Vantourout, Byron K. Peters, Yu Kawamata, Phil S. Baran
ACCOUNTS OF CHEMICAL RESEARCH
(2020)
Review
Chemistry, Multidisciplinary
Dillon T. Flood, Cian Kingston, Julien C. Vantourout, Philip E. Dawson, Phil S. Baran
ISRAEL JOURNAL OF CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Masato Saito, Yu Kawamata, Michael Meanwell, Rafael Navratil, Debora Chiodi, Ethan Carlson, Pengfei Hu, Longrui Chen, Sagar Udyavara, Cian Kingston, Mayank Tanwar, Sameer Tyagi, Bruce P. McKillican, Moses G. Gichinga, Michael A. Schmidt, Martin D. Eastgate, Massimiliano Lamberto, Chi He, Tianhua Tang, Christian A. Malapit, Matthew S. Sigman, Shelley D. Minteer, Matthew Neurock, Phil S. Baran
Summary: This translation discusses the importance of site-specific C-H bond oxidation in organic synthesis and the current limitations of chemical reagents in achieving this transformation. It introduces a platform using N-ammonium ylides as oxidants for site-specific, chemoselective C-H oxidation, which is guided by computation and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Jennifer M. Crawford, Cian Kingston, F. Dean Toste, Matthew S. Sigman
Summary: This article discusses the objectives and methods of asymmetric catalysis research. Researchers are dedicated to designing predictable catalysts, and have proposed a data science workflow for asymmetric catalyst design through the study of the correlation between enantioselectivity data and reaction component attributes.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Biochemistry & Molecular Biology
Joseph Breheny, Cian Kingston, Robert Doran, Joao Anes, Marta Martins, Seamus Fanning, Patrick J. Guiry
Summary: This study reported the antibacterial and antifungal evaluation of a series of (+)-tanikolide analogues, with one analogue showing promising anti-methicillin-resistant Staphylococcus aureus activity, while two further analogues synthesized with a modified alkyl side chain exhibited decreased activity against the same microorganism.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Daniel Zell, Cian Kingston, Janis Jermaks, Sleight R. Smith, Natalie Seeger, Jana Wassmer, Lauren E. Sirois, Chong Han, Haiming Zhang, Matthew S. Sigman, Francis Gosselin
Summary: A method to selectively access tetrasubstituted alkenes via nickel-catalyzed Suzuki-Miyaura cross-couplings has been developed, allowing for selective synthesis of each product isomer by judicious choice of ligand and reaction conditions. High-throughput optimization of monophosphine ligands was guided by chemical space analysis, leading to yields up to 94% and diastereomeric ratios up to 99:1 Z/E. Detailed computational and mechanistic studies provided key insights into the isomerization process impacting selectivity in the cross-coupling.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Xin Li, Therese B. Brennan, Cian Kingston, Yannick Ortin, Patrick J. Guiry
Summary: The design and synthesis of a series of chiral pyrrolidine-substituted ferrocene-derived ligands are reported. These ligands demonstrated excellent performance in the Rh-catalyzed asymmetric hydrogenation reaction, achieving high conversions and impressive levels of enantioselectivity.
