Article
Chemistry, Multidisciplinary
Jing Ren, Feng-Huan Du, Meng-Cheng Jia, Ze-Nan Hu, Ze Chen, Chi Zhang
Summary: A new strategy for carbon-carbon bond scission and intramolecular ring expansion fluorination of unactivated cyclopropanes was reported in this study, using a new hypervalent fluoroiodane(III) reagent 1. The reagent, characterized by NMR spectroscopy and X-ray crystallography, was synthesized in three steps with good overall yield and demonstrated high stability due to a secondary I...O bonding interaction. The reaction proceeds via a carbocation intermediate combining with fluoride ion to generate the product, as shown by density functional theory calculations and experimental studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Fei Cong, Riccardo S. Mega, Jinhong Chen, Craig S. Day, Ruben Martin
Summary: In this study, we report a visible-light-mediated trifluoromethylation reaction of carbonyl-type compounds and unactivated olefins using copper as a catalyst. This reaction allows for the synthesis of valuable C(sp(3))-CF3 structures from easily accessible precursors under mild conditions, making it a complementary approach for late-stage functionalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Kangning Cao, Zhan-Ming Zhang, Junliang Zhang, Fener Chen
Summary: The study presents a highly selective Pd-catalyzed reaction for the synthesis of a series of chiral benzene-fused cyclic compounds in a convenient manner.
Article
Chemistry, Multidisciplinary
Huan Zhang, Enhui Wang, Shasha Geng, Zhengli Liu, Yun He, Qian Peng, Zhang Feng
Summary: The iron-catalyzed defluorosilylation reaction is an efficient, highly functional-group compatible, and stereo- and regioselective reaction that can be used for late-stage silylation of biologically relevant compounds, offering opportunities for applications in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
Article
Chemistry, Multidisciplinary
Qu-Ping Hu, Yu-Tao Liu, Yong-Ze Liu, Fei Pan
Summary: A method for the remote regioselective alkynylation of unactivated C(sp(3))-H bonds in diverse aliphatic amides by photogenerated amidyl radicals has been developed. The site-selectivity is dominated via a 1,5-hydrogen atom transfer (HAT) process of the amide. Mild reaction conditions and high regioselectivity are demonstrated in this methodology.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Eva Korytiakova, Andreas Reichl, Markus Mueller, Thomas Carell
Summary: Cellular DNA consists of four canonical nucleosides and 5-methylcytosine, with stem cells' genome containing three additional dC derivatives formed through oxidation reactions. These derivatives are believed to undergo a cycle of methylation, oxidation, and conversion back to dC within the genome.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Lin Zhu, Xiao Meng, Leipeng Xie, Qiuyang Shen, Wenyi Li, Lanlan Zhang, Chao Wang
Summary: In this study, a bidentate directing group-assisted Ni-catalyzed three component 1,2-carbosulfenylation reaction was reported, which allows for the transformation of unactivated alkenes using aryl/alkenylboronic acids and disulfide electrophiles. The reaction showed high levels of chemo- and regioselectivity and could introduce a wide range of aryl groups and sulfur moieties into homoallylic amines. Notably, it also enabled the synthesis of α,gamma-dibranched thiolamines with high diastereoselectivity and enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Yang Sik Yun, Claudia E. Berdugo-Diaz, David W. Flaherty
Summary: Biomass has received considerable attention as an alternative to petrochemicals in the production of valuable chemicals and fuels. This Perspective discusses significant advancements in understanding the reaction networks and mechanisms, reactive intermediates, and active site motifs for selective production of desired compounds through hydrogenolysis over heterogeneous catalysts. Continuing research into hydrogenolysis reactions faces current challenges and provides opportunities for future exploration.
Article
Chemistry, Applied
Hisanori Nambu, Ryoya Amano, Takafumi Tamura, Takayuki Yakura
Summary: This study describes the dirhodium(II)-catalyzed intramolecular insertion of aryldiazoacetates into unactivated primary C-H bonds. The reaction shows high selectivity and provides a direct route to 2-unsubstituted indane-1-carboxylates and specific isomers with ortho-substituted groups. Furthermore, a chemoselective C-H insertion reaction of aryldiazoacetate with a 1-oxyethyl substituent is achieved using a specific protecting group.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Jintao Wu, Zehui Peng, Tong Shen, Zhong-Quan Liu
Summary: In this study, a new method for the oxidative cleavage of C(2)=C(3)/C(2)-N bonds of indoles using electrochemistry as the driving force is reported. Compared to previous strategies, this method avoids the use of heavy metals or stoichiometric chemical oxidants, and features metal-free conditions, air as the oxidant, and easy scalability.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Multidisciplinary Sciences
Zishuo Zhang, Jintong Zhang, Quan Gao, Yu Zhou, Mingyu Yang, Haiqun Cao, Tingting Sun, Gen Luo, Zhi-Chao Cao
Summary: The study demonstrates a C(sp3)-C(sp2) cross-coupling via asymmetric activation of the aromatic C-O bond for the synthesis of alkylated, axially chiral biaryl compounds. This method offers promising potential for complex molecule synthesis and asymmetric catalysis through nickel catalysis with good enantiocontrol.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Parul Garg, Tavinder Singh, Anand Singh
Summary: This study describes the photochemical functionalization of alkoxyoxazoles with trimethylsilyl azide and N,N-dimethylanilines. These C-N bond forming reactions proceed with the assistance of organic dyes as photocatalyst and molecular oxygen, leading to oxidative ring-opening and access to novel chemical space. The unusual demethylative C-N bond formation in the case of N,N-dimethylanilines establishes a new reactivity pattern for these precursors.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Ruitao Wu, Kaitlyn R. Wiegand, Lichang Wang
Summary: This study focuses on the C-C bond cleavage of ethanol on Ir(100), using density functional theory calculations and the degree of dehydrogenation of reactant species to correlate the cleavage barrier and reaction energy. The results show that the cleavage barrier generally decreases with decreasing degree of dehydrogenation, with a local minimum around a specific degree. Additionally, oxygen atom in the reactive species plays a critical role in lowering the C-C bond cleavage barrier.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Zeqi Jiang, Sheng-Li Niu, Qiang Zeng, Qin Ouyang, Ying-Chun Chen, Qing Xiao
Summary: A novel Pd-catalyzed reaction has been developed for selective alkynylallylation of specific C-C sigma bonds in cyclopropenes, providing an efficient approach to highly functionalized dienynes. The reaction features fascinating atom and step economy and can produce gram-scale products using a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations suggest that the success of the reaction relies on the selective insertion of cyclopropene double bonds into the C-Pd bond of ambidentate Pd complex and subsequent nonclassical beta-C elimination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Megumi Noshita, Yuhei Shimizu, Hiroyuki Morimoto, Shuji Akai, Yoshitaka Hamashima, Noriyuki Ohneda, Hiromichi Odajima, Takashi Ohshima
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2019)
Review
Chemistry, Multidisciplinary
Yuta Kondo, Hiroyuki Morimoto, Takashi Ohshima
Article
Chemistry, Multidisciplinary
Ryohei Yonesaki, Ibuki Kusagawa, Hiroyuki Morimoto, Tamio Hayashi, Takashi Ohshima
CHEMISTRY-AN ASIAN JOURNAL
(2020)
Article
Chemistry, Organic
Yuta Kondo, Tetsuya Kadota, Yoshinobu Hirazawa, Kazuhiro Morisaki, Hiroyuki Morimoto, Takashi Ohshima
Review
Chemistry, Physical
Kazuhiro Morisaki, Hiroyuki Morimoto, Takashi Ohshima
Article
Chemistry, Organic
Tetsuya Kadota, Masanao Sawa, Yuta Kondo, Hiroyuki Morimoto, Takashi Ohshima
Summary: This study successfully achieved direct transformation of unprotected α-aminonitriles, streamlining the synthesis of unnatural amino acid derivatives and achieving the shortest one-pot stereoselective routes to a biologically active compound reported to date.
Article
Cell Biology
Tsukasa Shimauchi, Takuro Numaga-Tomita, Yuri Kato, Hiroyuki Morimoto, Kosuke Sakata, Ryosuke Matsukane, Akiyuki Nishimura, Kazuhiro Nishiyama, Atsushi Shibuta, Yutoku Horiuchi, Hitoshi Kurose, Sang Geon Kim, Yasuteru Urano, Takashi Ohshima, Motohiro Nishida
Summary: Inhibition of TRPC6 channel activity in vascular smooth muscle cells promotes blood flow recovery in peripheral artery disease. The drug 1-BP can inhibit this channel activity, leading to improved peripheral circulation and skeletal muscle mass. Additionally, 1-BP can increase vascular nitric oxide bioavailability and enhance blood flow recovery in patients with endothelial dysfunction.
Article
Chemistry, Organic
Yuta Kondo, Yoshinobu Hirazawa, Tetsuya Kadota, Koki Yamada, Kazuhiro Morisaki, Hiroyuki Morimoto, Takashi Ohshima
Summary: A one-pot catalytic synthesis method for alpha-tetrasubstituted amino acid derivatives via in situ generation of N-unsubstituted ketimines is reported. This approach avoids the need for isolating unstable ketimines, resulting in higher yields and streamlining the synthesis process of highly congested alpha-amino acid derivatives.
Article
Chemistry, Organic
Emna Mejri, Kosuke Higashida, Yuta Kondo, Anna Nawachi, Hiroyuki Morimoto, Takashi Ohshima, Masaya Sawamura, Yohei Shimizu
Summary: A photoinduced N-internal vicinal aminochlorination reaction of styrene-type terminal alkenes was developed. The reaction proceeded without any catalyst, and the use of N-chloro(fluorenoneimine) as both a photoactivatable aminating agent and a chlorinating agent was essential. The introduced imine moiety at the internal position of the alkenes could be hydrolyzed under mild conditions to provide versatile beta-chlorinated primary amines, which demonstrated synthetic utility in several transformations.
Letter
Chemistry, Physical
Koki Yamada, Yuta Kondo, Akihiko Kitamura, Tetsuya Kadota, Hiroyuki Morimoto, Takashi Ohshima
Summary: We present an organocatalyzed direct enantioselective hydrophosphonylation of N-unsubstituted ketimines, which allows for the synthesis of N-unprotected alpha-tetrasubstituted alpha-aminophosphonates without the need for protection/deprotection steps. The reaction is effective for both N-unsubstituted isatin-derived and trifluoromethyl ketimines, resulting in high product yields with excellent enantioselectivity. Additionally, we discuss the potential applications of this reaction and propose a transition state model.
Article
Chemistry, Organic
Yuta Kondo, Hiroyuki Morimoto, Takashi Ohshima
Summary: In this article, we summarize our recent efforts in developing catalytic methods for synthesizing N-unsubstituted ketimines and their applications in one-pot reactions for producing various nitrogen-containing compounds. The account provides detailed background, optimization, scope, and mechanistic information. We hope that this work will stimulate further studies on the implementation of N-unsubstituted ketimines.
Article
Chemistry, Medicinal
Lu Lin, Shunsuke Kataoka, Kiichi Hirayama, Ryozo Shibuya, Hiroyuki Morimoto, Takashi Ohshima
Summary: Catalytic control of chemoselectivity is crucial in the synthesis of highly functionalized compounds. In this study, highly O- and N-selective electrophilic activation of allylic alcohols and amines was achieved in Pd-catalyzed direct allylic alkylation. The N- selectivity is due to the selective activation of allylic amines with ammonium cations, and boronate formation accelerates the activation of allylic alcohols.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2023)
Review
Chemistry, Organic
Hiroyuki Morimoto
Summary: In this study, we reported our recent progress in greener catalytic synthetic methods of nitrogen-containing compounds using N-unprotected ketimines. We found that zinc catalysts can effectively promote the alkynylation of N-unprotected trifluoromethyl ketimines, leading to high-yielding products with broad functional group tolerance and unique chemoselectivity. Furthermore, we expanded the methodology to catalytic stereoselective addition reactions, resulting in the synthesis of α-tetrasubstituted amines in high yield and stereoselectivity using appropriate metal or organocatalysts.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2022)
Article
Chemistry, Organic
Hiroyuki Morimoto, Walaa Akkad, Toru Deguchi, Takashi Ohshima
