Article
Chemistry, Multidisciplinary
Guanjie Wang, Qiao-Chu Zhang, Chenlong Wei, Ye Zhang, Linxue Zhang, Juhui Huang, Donghui Wei, Zhenqian Fu, Wei Huang
Summary: Functionalized aldimines have been used as new 1,4-dipole precursors in carbene catalysis, leading to enantiodivergent organocatalysis for the synthesis of both (R)- and (S)- enantiomers of compounds with quaternary carbon centers. The key factors for controlling enantioselectivity were found to be hydrogen bond C-H...F interactions between catalyst and substrate. These new 1,4-dipoles can also react with isatin and its imines under carbene catalysis, producing spiro oxindoles with excellent enantiomeric ratios.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wenxin Lu, Yongmei Zhao, Fanke Meng
Summary: This study presents the catalytic sequential hydrosilylation of 1,3-enynes and 1,4-enynes promoted by cobalt complexes derived from bisphosphines. The reactions resulted in the formation of enantioenriched cyclic alkenylsilanes with simultaneous construction of a carbon-stereogenic center and a silicon-stereogenic center. The functionalization of these chiral silanes provides access to a variety of difficult-to-access chiral building blocks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Chada Raji Reddy, Muppidi Subbarao, Anjali Rathaur, Ejjirotu Srinivasu
Summary: This paper reports the Rh(III)-catalyzed cascade oxidative C-H functionalization/aza-annulation of indole and pyrrole-N-carboxamides with 1,3-enynes involving 1,4-rhodium migration. It provides an approach for the synthesis of imidazo[1,5-a]indol-3(2H)-ones from easily accessible substrates. The compatibility of sulfonamides in this method is also demonstrated, leading to the corresponding benzo[d]sultams.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Takeshi Yasui, Yuya Nakazato, Koutarou Kurisaki, Yoshihiko Yamamoto
Summary: In this study, a Rh-catalyzed asymmetric [2+2+2] cycloaddition reaction was reported, resulting in the synthesis of enantio-enriched tricyclic cyclohexadienes with a quaternary bridgehead carbon. It was found that the Rh-Phanephos complex was the most suitable catalyst, while Rh-biaryl bisphosphine catalysts were not applicable.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Chunxiang Pan, Gaowei Wang, Hengyuan Zhao, Jianxiao Ni, Ruifeng Fan, Yongyun Zhou, Yuanbin Zhu, Shiyuan Wu, Baomin Fan
Summary: An efficient stereoselective cobalt-catalyzed hydrovinylative cyclization of 1,6-enynes with chalcones to obtain functionalized pyrrolidines has been developed. The products were furnished in good yields with up to 93% ee. A plausible mechanism through which the transformation was initiated by cyclization of 1,6-enynes is proposed.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Fang Hu, Yunpeng Chu, Zhengqiang Cao, Yucheng Li, Xin-Ping Hui
Summary: An efficient method utilizing the in situ generation of C-nucleophiles by an iridium catalyst in an asymmetric formal [5+1] annulation reaction has been developed for the synthesis of tetrahydropyridine derivatives. This methodology allows for the direct synthesis of a wide range of chiral tetrahydropyridine derivatives with moderate to good yields and excellent enantioselectivity.
Article
Chemistry, Applied
Yunhe Lv, Jinhui Xie, Weiya Pu, Xue Wang, Huanhuan Zhang, Xuerui Li, Yan Liu, Fei Chen, Yunfeng Xu
Summary: We developed a strategy for the copper-catalyzed three-component reaction to synthesize tetrasubstituted allenes with phosphinoyl and cyano groups. The reaction exhibited high functional group compatibility and good yields under mild conditions. A preliminary reaction mechanism involving the formation of phosphinoyl radicals and their regioselective addition to 1,3-enynes was proposed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Undamatla Suri Babu, Maneesh Kumar Reddy Singam, Muniganti Naveen Kumar, Jagadeesh Babu Nanubolu, Maddi Sridhar Reddy
Summary: This article presents a general approach to the synthesis of napthyridinones through the Pd-catalyzed annulation of 1,6-enynes with 2-iodoanilines. The protocol involves a rare carbo-aminative cyclization via the 6-endo-trig mode, and overcomes the commonly observed exo-trig/dig cyclizations. The regioselective aryl palladation of alkyne followed by intramolecular Heck-type reaction enables the cascade synthesis.
Article
Chemistry, Multidisciplinary
Linwei Zeng, Jiaming Li, Sunliang Cui
Summary: In this study, we report a rhodium-catalyzed enantioselective click cycloaddition of azides and alkynes, which allows for the rapid and modular synthesis of atropisomeric triazoles with excellent yields and enantioselectivities. The process is mild, efficient, scalable, and has a broad substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qi Cui, Zi-You Tian, Zhi-Xiang Yu
Summary: The unexpected three-component [4+2+1] reaction between two vinylallenes and CO was discovered to give highly functionalized tropone derivatives under mild conditions, where one vinylallene acts as a C-4 synthon, the other vinylallene as a C-2 synthon, and CO as a C-1 synthon.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Rajib Sarkar, Binoyargha Dam, Lenida Kyndiah, Fillip Kumar Sarkar, Sushmita Gajurel, Amarta Kumar Pal
Summary: Graphite oxide (GO) was developed from cheap and readily available graphite powder and used as a green heterogeneous carbocatalyst towards the synthesis of spirodibenzo[1,4]diazepine derivatives via a one-pot three-component strategy. The reaction conditions were mild and performed in aqueous ethanol medium, leading to diversely functionalized target products. The catalyst showed high catalytic activity and could be reused up to eight consecutive cycles without significant loss. The use of GO as a metal-free catalyst avoids metal impurities in the final products.
Article
Chemistry, Multidisciplinary
William G. Whitehurst, Junho Kim, Stefan G. Koenig, Paul J. Chirik
Summary: A cobalt-catalyzed intermolecular three-component coupling of arenes, ethylene, and alkynes was developed using a stable air-stable cationic bis(phosphine) cobalt(I) complex as the precatalyst. The method exhibited good functional group tolerance and allows for late-stage functionalization of drug molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Tao Wang, Ji-Xun Guan, Yun-Xuan Tan, Ping Tian
Summary: This paper reports the first cobalt-catalyzed highly selective arylation carbocyclization reaction of 1,6-allenynes with arylboronic acids. The reaction demonstrates moderate to high yields, broad substrate scope, and good compatibility with functional groups.
Article
Chemistry, Physical
John M. Halford-McGuff, Alexandra M. Z. Slawin, Allan J. B. Watson
Summary: This article presents a predictive model for the reactivity and turnover of the Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes. Contrary to the proposed electronic model, this model suggests that the reaction is predominantly driven by steric effects, and turnover is proportional to alkyne steric parameters. The model allows for the prediction of catalyst loading, turnover, and reaction yield based on the assessment of the alkyne's steric parameter.
Article
Chemistry, Multidisciplinary
Mitsuhiro Ueda, Kazuya Kamikawa, Takahide Fukuyama, Yi-Ting Wang, Yen-Ku Wu, Ilhyong Ryu
Summary: A novel method has been developed for site-selective alkenylation of a broad variety of substrates, including sterically hindered acyclic and alicyclic substrates. This method allows for the generation of (E)-2-alkylvinylphenylsulfones in high yield by utilizing persulfate and 1,2-bis(phenylsulfonyl)ethene. The compact size of the sulfate radical employed in C-H activation and cleavage allows for the alkenylation of sterically hindered C-H bonds, broadening the scope of substrates that can be efficiently transformed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Nene Soga, Tomo Yoshiki, Aoi Sato, Takuji Kawamoto, Ilhyong Ryu, Hiroshi Matsubara
Summary: In this study, borane was generated in situ using a PV method from NaBH4 or (Bu4NBH4)-Bu-n and reacted with alkenes to produce alcohols. The evolved borane was also used for selective reduction of carboxylic acids and successful Suzuki-Miyaura coupling. The PV system allowed easy and safe reactions with borane in common test tubes.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Applied
Yi-Ting Wang, Yi-Lun Shih, Yen-Ku Wu, Ilhyong Ryu
Summary: Site-selective C(sp(3))-H alkenylation was achieved under photo-irradiation in the presence of a catalytic decatungstate anion. The reaction successfully combines radical addition/beta-scission sequence with photocatalytic C(sp(3))-H functionalization. The decatungstate anion participates in a chain-repairing step in reactions with weaker C-H bonds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Takayoshi Kasakado, Takahide Fukuyama, Tomohiro Nakagawa, Shinji Taguchi, Ilhyong Ryu
Summary: This study reports the high-speed C-H chlorination of ethylene carbonate and introduces a photoflow setup for gas-liquid biphasic reactions. The direct use of chlorine gas and the photoirradiation conditions affect the selectivity of the product.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Takahide Fukuyama, Takayoshi Kasakado, Mamoru Hyodo, Ilhyong Ryu
Summary: In this article, we discuss the effectiveness of photo-induced organic reactions when using evolving photo flow technologies. By updating the flow reactors and light sources, the energy profile of the reactions improved significantly. We successfully applied photo flow technologies in various reactions, such as isomerization, alkylation, radical cyclization, and oxidation.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2022)
Article
Chemistry, Applied
Takashi Kuwahara, Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: The RuHCl(CO)(PPh3)(3)-catalyzed cross-coupling reaction has been extended to synthesize 1,3-diaryl 1,3-diketones, and also applied to the synthesis of PPT (propyl pyrazole triol). A study revealed the formation of a five-membered ruthenacycle, beta-ruthenium ketone, during the reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Yi-Lun Shih, Yen-Ku Wu, Mamoru Hyodo, Ilhyong Ryu
Summary: A catalytic amount of decatungstate photocatalyst under black light irradiation was able to promote the oxidative cleavage of C=C bonds with molecular oxygen, resulting in the formation of both aromatic and aliphatic ketones. The use of a high-power ultraviolet light-emitting diode at 365 nm for the continuous flow reaction of alpha-methylstyrene significantly reduced the reaction time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shuhei Sumino, Ilhyong Ryu
Summary: The radical bromoallylation of alkynes, allenes, and vinylidene cyclopropanes can proceed efficiently in the presence of a radical initiator to give different diene derivatives. Three-component reactions involving allenes, electron-deficient alkenes, and allyl bromides can provide good yields of 1,7-dienes. The reaction of arylalkenes with allyl bromides can selectively produce 5-bromoalkenes, while the bromoallylation of vinylcyclopropanes results in 5-exo ring closure to yield 1-(bromomethyl)-2-vinylcyclopentane derivatives with high yields. All of the products contain a reactive vinyl bromide moiety, which can be easily functionalized through Pd-catalyzed cross-coupling and radical cascade reactions.
Review
Chemistry, Physical
Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This paper summarizes our team's efforts over the past two decades in the development of new catalytic methods for C-C bond formation. The versatile applications of the commercially available catalyst RuHCl(CO)(PPh3)(3) (or RuH for short) are highlighted through eight different transformations. The fundamental steps involved in the catalysis are emphasized, demonstrating how our mechanistic understanding and the diverse catalytic capabilities of RuH can be utilized to design desired catalytic cycles and develop new cross-coupling reactions with high atom-economy.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Applied
Takahide Fukuyama, Takashi Kuwahara, Yuki Yamamoto, Baptiste Picard, Ilhyong Ryu
Summary: The selective olefin isomerization of homoallyl silyl ethers and carbonates was investigated by utilizing RuHCl(CO)(PPh3)(3) as the catalyst. It was found that the presence of an aryl or alkyl substituent at the α-position to the oxygen atom led to selective conversion to allyl silyl ethers, while no substituent at the α-position resulted in isomerization to enol silyl ethers. In contrast, the isomerization of homoallyl carbonates gave the corresponding allyl carbonates selectively regardless of the substituent at the α-position.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chen-Yang Tsai, Yin-Jia Jhang, Yen-Ku Wu, Ilhyong Ryu
Summary: This study reports a protocol for alkene hydroxyalkenylation and a photocatalytic protocol for alkoxyalkenylation. Alkenes can be converted into the corresponding 1-phenylsulfonyl-4-hydroxyalkenes or alkoxyalkenes in good to high yields using a persulfate anion as an oxidation reagent and 1,2-bis(phenylsulfonyl)ethylene as a radical acceptor. The methods exhibit wide substrate adaptability and regioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nobukazu Taniguchi, Mamoru Hyodo, Lin-Wei Pan, Ilhyong Ryu
Summary: Site-selective C(sp(3))-H thiolation has been achieved using thiosulfonates as substrates and the decatungstate anion as a photocatalyst. The reaction proceeds through a cascade of double S(H)2 reactions, HAT and ArS group transfer, and PCET, allowing the recovery of the catalyst, W10O324-.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Ryo Takabayashi, Stephan Feser, Hiroshi Yonehara, Ilhyong Ryu, Takahide Fukuyama
Summary: In this study, it was found that nitroxide-mediated radical polymerization (NMP) using BlocBuilder MA under continuous flow reaction conditions led to higher conversions and smaller polydispersity index (D) values compared to batch reaction conditions. The addition of a small amount of acetol or malononitrile accelerated the NMP reaction without sacrificing the quality of the polymer. Flow reactors allowed for precise control of the NMP process initiated by BlocBuilder MA and the synthesis of di-block copolymers.
Review
Chemistry, Multidisciplinary
Takuji Kawamoto, Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This feature article highlights the powerful methods of radical carbonylation and our current efforts in developing new strategies for this reaction.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
