Article
Chemistry, Applied
Christoph Middel, Lukas Zygalski, Jannick Meinecke, Ulrich Koert
Summary: The rhodium-catalyzed allylic cyanation of 3-fluoroallylic trifluoroacetates with TMSCN and a bulky phosphite ligand efficiently produces 3-fluoroallylic nitriles with a wide substrate scope and high Z/E-selectivity. The fluorine substituent controls the regioselectivity in favor of the distal product for dialkylated substrates. Selected scalemic substrates show inversion of stereocenter and minimal or no stereoerosion in the stereoselectivity of allylic cyanation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Letter
Green & Sustainable Science & Technology
L. Reijnders
Summary: The study suggests that copper substitutability may be as high as 60% or more of current copper use, far exceeding previous estimates.
JOURNAL OF CLEANER PRODUCTION
(2021)
Article
Chemistry, Organic
Viktor V. Khutorianskyi, Norbert Baris, Petr Beier
Summary: The oxidative nucleophilic aromatic substitution of hydrogen in nitroaromatics with potassium alkoxides derived from primary, secondary, or tertiary alcohols in the presence of oxygen was achieved. The products showed good reactivity in nucleophilic aromatic substitution of the nitro group with oxygen or nitrogen nucleophiles to access selectively substituted aromatic compounds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Siju Bi, Wenshuang Diao, Ting Tian, Ting Zhou, Kuaile Lin, Weicheng Zhou
Summary: A new method was developed to synthesize 5-Fluoro-1-(2-fluorobenzyl)-1H-pyrazolo[3,4-b]pyridine-3-carbonitrile (9) from 2-chloro-5-fluoronicotinic acid (22) with a yield of 48.3%. The intermediate compounds 26, 27, and 28 were obtained and their structures were confirmed through various analytical techniques. Key intermediate 9 was synthesized through Pd-catalyzed cyanation of compound 28.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Multidisciplinary
Sandip Mondal, Gobinda Dolai, Bhubaneswar Mandal
Summary: The sulfonic acid functionalization of electron-deficient benzene sulfonic acids allows ipso nucleophilic substitution with active methylene compounds, resulting in new C-C bond formation. This method provides good to excellent yields under mild conditions without the need for transition-metal catalysts, PTC, and ligand. It offers a novel approach to incorporate various active methylene compounds into the o-nitro-substituted benzene ring and has potential applications in API synthesis and materials chemistry. The discovery of carbon-carbon bond formation by substituting a sulfonic acid group is significant.
Article
Chemistry, Multidisciplinary
Youhao Wei, Zheng Wang, Kaifeng Wang, Jiang-Kai Qiu, Zhaoshan Wang, Haotian Li, Xiu Duan, Kai Guo, Xiaoguang Bao, Xinxin Wu
Summary: This study reports a copper-catalyzed allenic C(sp(2))-H cyanation with exceptional site-selectivity, addressing the challenge in synthetic chemistry of functionalizing allenic C(sp(2))-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
G. Sudhakar Reddy, E. J. Corey
Summary: This article presents short synthetic routes to the nonplanar tetracyclic ketiminium salt A and two similar compounds. X-ray crystallography confirms their helical nonplanar structures.
Article
Chemistry, Multidisciplinary
Tao He, Guoqiang Wang, Peng-Wei Long, Sebastian Kemper, Elisabeth Irran, Hendrik F. T. Klare, Martin Oestreich
Summary: A trityl-cation-initiated annulation of benzyl-substituted vinylcyclopropanes with hydrosilanes has been reported, leading to the formation of new Si-C(sp(3)) and C(sp(2))-C(sp(3)) bonds through intramolecular reactions. The reaction mechanism proposed based on computations is in agreement with experimental observations, resulting in the formation of unprecedented silicon-containing fused ring systems. Another tricycle with a 6/6/6 ring fusion structure was obtained from a phenethyl-substituted VCP derivative through a related but different reaction pathway.
Article
Polymer Science
Naoki Shida, Kazuyuki Ninomiya, Natsuki Takigawa, Keiichi Imato, Yousuke Ooyama, Ikuyoshi Tomita, Shinsuke Inagi
Summary: A postpolymerization nucleophilic aromatic substitution reaction is used to efficiently diversify conjugated polymers, with complete substitution achieved by thiophenol derivatives and carbazole, while disubstitution occurs with para-selectivity by phenol derivatives.
Article
Chemistry, Organic
Chunxiang Pan, Chunhui Yang, Kangkui Li, Keyang Zhang, Yuanbin Zhu, Shiyuan Wu, Yongyun Zhou, Baomin Fan
Summary: An efficient, catalyst/photocatalyst-free, and cost-effective methodology has been developed for the synthesis of beta,gamma-unsaturated nitriles from alpha,beta-unsaturated carboxylic acids. The reaction proceeded in an environmentally benign atmosphere of blue light-emitting diode irradiation with K2CO3 and water at room temperature, showing high yields (up to 83%) with a wide range of substrates.
Article
Multidisciplinary Sciences
Hui Cao, Qiang Cheng, Armido Studer
Summary: This article introduces a highly selective method for functionalization of pyridines at the meta position, achieving trifluoromethylation, perfluoroalkylation, chlorination, bromination, iodination, nitration, sulfanylation, and selenylation through a dearomatization-rearomatization process. The method can be applied for late-stage functionalization of drugs.
Article
Chemistry, Organic
Ling Luo, Jin-Hong Lin, Ji-Chang Xiao
Summary: A Ph3P/ICH2CH2I-promoted dehydroxylative cyanation of alcohols has been developed, which offers convenient operations, mild reaction conditions, and the use of cheap and widely available reagents, avoiding the limitations of previous methods that involve transition metals or moisture-sensitive Lewis acids.
Article
Chemistry, Organic
Sha Peng, Luo Yang
Summary: A practical and convenient copper-catalyzed method for cyanation of aryl iodides using formamide as the cyano source has been developed. This method offers high yields of various aryl nitriles, and its lower reaction temperature and excellent substrate compatibility make it more attractive in synthetic and pharmaceutical chemistry.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Correction
Chemistry, Multidisciplinary
Kun-Xu Teng, Li-Ya Niu, Yan-Fei Kang, Qing-Zheng Yang
Summary: This study discusses a rational design of a dual lock-and-key supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy.
Article
Chemistry, Multidisciplinary
Eduardo Rodrigo, Rainer Wiechert, Magnus W. Walter, Wilfried Braje, Herve Geneste
Summary: By using KOH, the direct F to OH exchange of aromatic and heteroaromatic substrates can be achieved under mechanochemical conditions, making the process more atom economical and environmentally friendly compared to other methods.
