Article
Multidisciplinary Sciences
Zhiguo Zhao, Yuanling Pang, Ziqiang Zhao, Pan-Pan Zhou, Yao Wang
Summary: The activation of ethers by weak interactions in supramolecular catalysis remains challenging. In this study, the authors describe an activation mode based on dual Se···π and Se···O bonding, that can activate benzylic as well as allylic ether C-O σ-bonds to achieve cyclization, coupling and elimination reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Xiuli Wu, Yaxin Zeng, Zhong-Tao Jiang, Yulei Zhu, Linshen Xie, Ying Xia
Summary: This article reports a Lewis acid-catalyzed cross-coupling reaction of gem-difluorinated cyclopropanes with nucleophiles, in which the C-F bond is activated to generate a fluoroallyl cation species that is then trapped by nucleophiles to give fluoroallylic products in good yields.
Article
Chemistry, Multidisciplinary
Damian Antoniak, Bartosz Paluba, Tymoteusz Basak, Kacper Blaziak, Michal Barbasiewicz
Summary: The alkylation of nitroarenes via Vicarious Nucleophilic Substitution (VNS) was experimentally tested and modeled with DFT calculations. Mechanistic studies showed intrinsic differences between the reactions of the carbanion precursor PhSO2CH2Cl and alkyl phenyl sulfones with benzenesulfinate as a leaving group. Steric hindrance developed at the beta-elimination step for the latter precursors, raising the energy barrier and resulting in the formation of byproducts.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Woohyun Jo, Jun Hee Lee, Seung Hwan Cho
Summary: This feature article summarises recent progress in the synthetic utilisation of alpha-borylcarbanions, including carbon-carbon bond formation with alkyl halides, alkenes, N-heteroarenes, and carbonyls. Carbon-boron bond formation in organohalides mediated by alpha-borylcarbanions is also summarised.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Xiao-Lan Liu, Luo-Bin Jiang, Mu-Peng Luo, Zhi Ren, Shou-Guo Wang
Summary: This review summarizes the rapid progress in the catalytic asymmetric C-H functionalization of N-containing heteroarenes and discusses the challenges and potential of the field in the current stage.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Peiying Li, Rong Chang, Fujun Guan, Wenjing Yang, Cong-Ying Zhou, Zhen Guo
Summary: Here, we demonstrate the heterogeneous photocatalytic C-Halkylation of indoles with diazo compounds using graphitic carbonnitride (g-C3N4) as the stable and reusable catalyst. The reaction proceeds under simple and mild conditions, and involves a photochemical process mediated by a carbon radical generated from the diazo compounds via visible-light-promoted proton-coupled electron transfer (PCET).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiaolu Wen, Min Gao, Yiwei Chen, Yukun Zhao, Wenling Qin, Lin Hu
Summary: A new annulation reaction between allylic/benzylic peroxides and ketones has been developed, providing moderate yields of α-oxacyclic ketones under (KOBu)-Bu-t basic conditions. Mechanistic studies reveal that these peroxides undergo the Komblum-DeLaMare rearrangement, releasing aldehyde intermediates and initiating the aldol/etherification tandem process for product formation. Moreover, these peroxides, acting as masked enals, have also been used to synthesize α-enal-tethered ketones, which were previously difficult to achieve in one step.
Article
Chemistry, Organic
Shinyeong Han, Injoo Seo, Do Hyun Ryu
Summary: A catalytic enantioselective Friedel-Crafts reaction of various heteroaromatic compounds with glyoxals has been developed, providing chiral alpha-hydroxyketones in high yield and excellent enantioselectivity. The synthetic utility of this method was demonstrated by converting the products to various derivatives such as 1,2-diol and optically active amino alcohol.
Article
Chemistry, Organic
Chang-Yun Shi, Xiao-Qu Chen, Ruoqing Zeng, Heng Lu, Zhoulong Fan, Ao Zhang
Summary: This study presents a new approach to difluoroallylation using ruthenium catalysis, which enables the regiodivergent C-H alpha,alpha- and ortho C-H gamma,gamma-difluoroallylation of arenes.
Article
Chemistry, Multidisciplinary
Wan-Xu Wei, Yuke Li, Ya-Ting Wen, Ming Li, Xue-Song Li, Cui-Tian Wang, Hong-Chao Liu, Yu Xia, Bo-Sheng Zhang, Rui-Qiang Jiao, Yong-Min Liang
Summary: This study reports a method for the synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem reaction, with the key step involving the activation of the δ-C-H bond to form a five-membered spiro-palladacycle intermediate. The CMD process, rate-determining step, and energy barrier of the entire reaction were explored through DFT calculations. Control experiments were conducted to investigate the rate-determining step and reversibility of the C(sp(3))-H activation step.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Shitao Pan, Qiqiang Xie, Xiu Wang, Qian Wang, Chuanfa Ni, Jinbo Hu
Summary: The TMSCF3-derived CuCF2CF3 species has been successfully utilized for the pentafluoroethylation of organoboronates and terminal alkynes. With 1,10-phenanthroline as a ligand, a wide range of (hetero)arylboronates and alkenylboronates can be smoothly pentafluoroethylated under aerobic conditions. Furthermore, terminal alkynes can undergo aerobic cross-coupling with the TMSCF3-derived CuCF2CF3 species without the need for additional ligands.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: This study reveals a novel iron-catalyzed para-C-H allylation reaction of aniline derivatives via a chelation-induced strategy, providing various allylic arenes with good yields and selectivity.
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: Transition-metal-catalyzed directed C-H allylation of arenes is an efficient method to construct value-added allylic arenes. This study presents a novel iron catalyst and a chelation-induced strategy for the para-C-H allylation of aniline derivatives, which provides good yields and excellent selectivity.
Article
Chemistry, Organic
Hao Xu, Xufeng Li, Yuzheng Dong, Shuangran Ji, Junze Zuo, Jian Lv, Daoshan Yang
Summary: An efficient strategy for the preparation of aryl phosphonates has been demonstrated via a blue-light-promoted single electron transfer process of an EDA complex. The method enables the construction of aryl phosphonates through the indirect C-H functionalization of arenes, leading to good to excellent yields of substituted aryl phosphonates and the recovery and reuse of the byproduct thianthrene. This approach has potential application value in drug discovery and development.
Article
Chemistry, Organic
Shang-Shi Zhang, Yi-Chuan Zheng, Zi-Wu Zhang, Shao-Yong Chen, Hui Xie, Bing Shu, Jia-Lin Song, Yan-Zhi Liu, Yao-Fu Zeng, Luyong Zhang
Summary: A novel rhodium(III)-catalyzed C-H allylation reaction has been developed using 2-methylidenetrimethylene carbonate as an efficient allylic source, resulting in the synthesis of various branched allylarenes bearing an allylic hydroxyl group in moderate to excellent yields. Five different directing groups, including oxime, N-nitroso, purine, pyridine, and pyrimidine, were found to be compatible in this reaction.
Article
Chemistry, Inorganic & Nuclear
Shoji Kataoka, Hiroki Fukumoto, Tomoko Kawasaki-Takasuka, Takashi Yamazaki, Katsuyuki Nishimura, Tomohiro Agou, Toshio Kubota
JOURNAL OF FLUORINE CHEMISTRY
(2019)
Article
Chemistry, Organic
Riku Shinohara, Masao Morita, Narihito Ogawa, Yuichi Kobayashi
Article
Chemistry, Organic
Yuji Tamura, Rina Yada, Tomoko Kawasaki-Takasuka, Tomohiro Agou, Toshio Kubota, Takashi Yamazaki
Article
Polymer Science
Tomohiro Agou, Kazuto Yoshinari, Tomohiro Shirai, Shigeyuki Yamada, Tsutomu Konno, Yoshiyuki Mizuhata, Norihiro Tokitoh, Sana Yasuda, Takashi Yamazaki, Hiroki Fukumoto, Toshio Kubota
Article
Chemistry, Organic
Narihito Ogawa, Ryoya Imaizumi
Article
Chemistry, Organic
Yasutaka Shimotori, Masayuki Hoshi, Narihito Ogawa, Tetsuo Miyakoshi, Taisei Kanamoto
HETEROCYCLIC COMMUNICATIONS
(2020)
Article
Chemistry, Organic
Narihito Ogawa, Shinsaku Sone, Song Hong, Yan Lu, Yuichi Kobayashi
Article
Chemistry, Organic
Takashi Yamazaki, Yoh Nakajima, Minato Iida, Tomoko Kawasaki-Takasuka
Summary: The study presents a concise method for preparing 4,4,4-trifluorobut-2-yn-1-ones by oxidizing readily accessible propargylic alcohols, and demonstrates their use as Michael acceptors for constructing aromatic and heteroaromatic compounds.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Takashi Yamazaki, Masahito Taketsugi, Tomoko Kawasaki-Takasuka, Tomohiro Agou, Toshio Kubota
Summary: Using CuBr·SMe2 and TMSCl as catalysts, Michael addition reactions of various Grignard reagents to 4,4,4-trifluorinated alpha, beta-unsaturated carboxylic acid derivatives with 4-substituted oxazolidin-2-ones as a chiral auxiliary proceed smoothly to construct the desired products with quaternary stereocenters possessing a CF3 group in good to excellent yields.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Biochemistry & Molecular Biology
Yoko Hamada, Rio Matsunaga, Tomoko Kawasaki-Takasuka, Takashi Yamazaki
Summary: The CF3 group was found to significantly influence the base-mediated proton shift in propargylic or allylic alcohols with high CF3 content, allowing for the synthesis of alpha, beta-unsaturated or saturated ketones. This method was applied to the synthesis of allyl vinyl ethers in this study, achieving the desired rearrangement through proton shift.
Article
Chemistry, Organic
Kyu Terashima, Tomoko Kawasaki-Takasuka, Ichiro Minami, Takashi Yamazaki
Summary: A convenient method for synthesizing (hydroxyphenyl)perfluoro-alkylmethanols was developed by utilizing the Meerwein-Ponndorf-Verley (MPV) type reduction. The key step involved the in situ generation of perfluoroalkylated ketones. The resulting alcohols underwent successful transformation of the benzylic OH group to H or Rf(CH2)(n)O via the corresponding chlorides, a conversion not easily achieved by other methods.
Article
Chemistry, Inorganic & Nuclear
Takashi Yamazaki, Minato Iida, Tomoko Kawasaki-Takasuka, Tomohiro Agou
Summary: The utilization of 3,3,3-trifluoroprop-1-yne in the presence of BF3·OEt2 was demonstrated to achieve regio- and stereoselective ring opening of various epoxides, leading to the synthesis of CF3-containing homopropargylic alcohols in high yields.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Organic
Kyu Terashima, Tomoko Kawasaki-Takasuka, Takashi Yamazaki
Summary: The 1,6-conjugate additions of in situ generated delta-CF3-delta-substituted p-quinone methides with various heteronucleophiles under mild conditions successfully led to the construction of fully substituted carbon centers, including a heteroatom and a CF3 group. It was also discovered that some amines can efficiently cleave the TBS protective group, and the addition of a catalytic amount of an appropriate Bronsted acid can enhance the progress of the desired process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Kyu Terashima, Tomoko Kawasaki-Takasuka, Tomohiro Agou, Toshio Kubota, Takashi Yamazaki
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Kyu Terashima, Tomoko Kawasaki-Takasuka, Tomohiro Agou, Toshio Kubota, Takashi Yamazaki
CHEMICAL COMMUNICATIONS
(2020)