Article
Chemistry, Organic
Belen Rubial, Alfredo Ballesteros, Jose M. Gonzalez
Summary: The addition of catalytic amounts of bistriflimide triggers useful coupling reactions between benzyl acetates and trimethyl(alkynyl)silanes as well as trimethyl(alkoxy)silanes, resulting in the formation of propargyl arenes and benzyl alkyl ethers, respectively. The added acid facilitates the release of reactive trimethylsilylium ion into the reaction media, which acts as the ultimate catalytic species responsible for the formation of C-C and C-O bonds. The cationic nature of these coupling processes is confirmed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ryoga Oda, Kenya Nakata
Summary: The nucleophilic substitutions of benzylic alcohols with sulfamides were successfully achieved using an FeCl3 Lewis acid catalyst in MeNO2. The reaction conditions needed to be adjusted depending on the stability of the carbocation intermediates to obtain efficient yields. Various diarylmethanols and benzylic alcohols were applicable to the reaction, and the sulfamide moieties could be easily deprotected and converted into amine groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yupian Deng, Ying Liu, Jingjing He, Pai Zheng, Zhudi Sun, Song Cao
Summary: An efficient and practical method was developed for synthesizing functionalized trifluoromethyl cyclopropanes through cyclopropanation of α-trifluoromethyl styrenes with chloroacetonitrile or ethyl chloroacetate. In some cases, the trans- and cis-isomers could be separated by column chromatography. The configurations of the trans-/cis-isomers were further confirmed by heteronuclear H-1-F-19 NOESY experiments.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Polymer Science
Minoru Koyama, Midori Akiyama, Kimiaki Kashiwagi, Kyoko Nozaki, Takashi Okazoe
Summary: In this study, a CF3-rich perfluoropolyether (PFPE) with a crystalline structure was successfully synthesized. This solid PFPE exhibited higher water- and oil-repellency compared to polytetrafluoroethylene (PTFE).
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Can-Can Bao, Yan-Long Luo, Hui-Zhen Du, Bing-Tao Guan
Summary: The study reported a method using LDA-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides, providing an efficient synthesis of various aryl benzyl ketones.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Organic
Wei Wang, Zhaoliang Qin, Ze Tan, Wen Yang
Summary: An efficient organocatalytic enantioselective cross-aldol reaction of aryl ketones with heteroaromatic trifluoromethyl ketone hydrates via enolate intermediates has been developed. The cross-aldol reactions catalyzed by Takemoto-type thiourea catalysts proceeded well under mild conditions, furnishing a variety of enantioenriched alpha-trifluoromethyl tertiary alcohols bearing N-heteroaromatics with good to high yields and enantioselectivities. This protocol features broad substrate scope, good functional group tolerance, and easy gram-scale preparation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hao Jia, Andreas P. Haering, Florian Berger, Li Zhang, Tobias Ritter
Summary: In this study, we report the synthesis and application of a novel trifluoromethylating reagent TT-CF3+OTf-, which can be used in various trifluoromethylation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xue-Hua Deng, Jia-Xi Jiang, Qin Jiang, Ting Yang, Bo Chen, Long He, Wen-Dao Chu, Cheng-Yu He, Quan-Zhong Liu
Summary: In this study, the asymmetric cross reductive coupling reaction of conjugated dienes and ketoimines using copper hydride as a catalyst was achieved for the first time. The reaction, catalyzed by chiral Ph-BPE ligand, provides a rapid and efficient access to homoallylic amines with two vicinal stereogenic centers.
Article
Biochemistry & Molecular Biology
Chris Douvris, David Matatov, Derek Bussan, Christos Lampropoulos, Donald J. Wink
Summary: Fluorochemistry is a rapidly advancing field with applications in materials, pharmaceuticals, and agriculture. Synthetic perfluorinated chemistry is particularly underdeveloped in the area of metal complexes, and this study focuses on the synthesis and characterization of a cyclohexadienyl metal complex containing a trifluoromethyl group. The use of Morrison's trifluormethylating reagent resulted in the successful synthesis of the complex, which was characterized using various techniques including X-ray crystallography.
Article
Chemistry, Multidisciplinary
Woohyung Jeon, Ramil Baiazitov, Matteo Chierchia, Kyle Niederer, Hongyu Ren, Young-Choon Moon, Bradley B. Gilbert
Summary: This article reports a simple synthetic method for preparing various di- and trifluoromethyl-s-triazines from readily available starting materials. Trichloromethyl-substituted triazine electrophiles were obtained in good yield and reacted with amine nucleophiles to afford aminotriazine products in good to excellent yield. The nucleophilic aromatic substitution reaction showed broad scope, smoothly proceeding with both aromatic and aliphatic amines in the presence of non-participating functional groups, and requiring only a catalytic amount of 4-DMAP without stoichiometric base.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Wen Wang, Yang Deng, Rui-Xue Li, Jin-Feng Lv, Ming-Qiu-Hao Fu, Zhi Guan, Ya-Nan Zhao, Yan-Hong He
Summary: Here, we report the first electrochemical strategy for direct acyloxylation of benzylic C(sp3)-H with amides. The method offers transition metal and oxidant-free conditions with H2 evolution, excellent tolerance towards various functional groups, and high yields up to 82% in an operation-friendly undivided cell. Mechanistic experiments confirm the involvement of radicals and the breaking of the amide C-N bond.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Organic
Jiayu Alicia Lim, Yong-Chua Teo
Summary: This paper demonstrated a new and economical methodology using Fe(ClO4)(2)center dot H2O as a catalyst for the direct C(sp(3))-H functionalization of 2-methyl azaarenes via addition to trifluoromethyl ketones. The use of Fe salts as a Lewis acid catalyst has shown great potential as an accessible, affordable, and effective catalyst for the reaction. Under mild, optimized conditions, an extensive range of 2-alkenylated azaarenes was produced with yields of up to 95%.
SYNTHETIC COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Feng Chen, Fuhai Li, Qingle Zeng
Summary: In this study, substituted dibenzyl diselenides were synthesized in good yields (74-91%) through S(N)2 nucleophilic substitution of benzylic trimethylammonium salts and diselenide dianion (Se2-) under basic conditions. Highly enantiopure dibenzylic diselenides (95-98% ee) with reverse configurations to their enantioenriched quaternary ammonium salts are obtained when benzylic quaternary ammonium salts, synthesized from enantiomerically enriched amines, are used.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Alisson Silva Granato, Giovanni Wilson Amarante, Javier Adrio
Summary: An environmentally friendly protocol for the generation of C-aryl nitrones from benzylic secondary amines using catalyst-free oxidation with H2O2 in MeOH or CH3CN is described. This method provides a selective access to a variety of C-aryl nitrones with yields ranging from 60% to 93%. Several studies have been conducted to elucidate the reaction mechanism and the role of the solvent.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Lu Chen, Xi Chen, Tingting Zhu, Haibing Shao, Zhihua Chen, Yan Hu, Zhenjiang Liu, Chuanxiang Liu
Summary: This study presents a novel synthesis method involving cyanide ion-promoted nucleophilic displacement without transition metal catalysts to create nitrile-containing naphthalimide aryl ether derivatives, offering a new pathway for the preparation of diaryl ether derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
