Article
Chemistry, Organic
Ryosuke Matsubara, Tatsuhiro Harada, Weibin Xie, Tatsushi Yabuta, Jiasheng Xu, Masahiko Hayashi
Summary: Organohydrides are important organic compounds that provide hydride anions for reactions, and their hydride transfer and regeneration play a crucial role in organohydride-catalyzed reduction reactions. In this study, different forms of BIH derivatives were synthesized and their photophysical and electrochemical properties were investigated. The 4-(dimethylamino)phenyl-substituted BIH showed red-shifted absorption and visible-light-driven regeneration without using an external photosensitizer. This has implications for the development of solar-energy-based catalytic photoreduction technologies.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chenhao Lou, Yuting Feng, Qiuwei Huang, Leiyang Lv, Zhiping Li
Summary: A visible light-induced decarboxylative peroxidation of carboxylic acids has been disclosed. With this protocol, a variety of readily available carboxylic acids were converted to the stabilized organic peroxides in moderate to good yields via decarboxylative radical C-OO bond coupling. Tert-butyl hydroperoxide acts as both the oxidant and peroxyl source, avoiding the use of transition metals or extra oxidants.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jing Li, Martin J. Lear, Yujiro Hayashi
Summary: A new transition metal-free synthesis method for cyclopropanes has been achieved, which tolerates various aryl systems, as well as sulfide or alkene functionality, to yield cis-aryl/cyano cyclopropanes bearing congested tetrasubstituted quaternary carbons.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Jan Bojanowski, Anna Albrecht
Summary: A new doubly decarboxylative Michael-type addition method has been developed for the synthesis of biologically relevant compounds in good yields. The decarboxylative reaction pathway has been confirmed through mechanistic studies, and an attempt to develop an enantioselective variant of the cascade has also been described.
Review
Chemistry, Applied
Cairong Wang, Ge Qiu, Chen Li, Kai Sun, Zhichuan Wang, Xin Wang
Summary: Carboxylic acid compounds are important structural units that exist widely in nature, and decarboxylative reactions have great significance in synthetic chemistry due to the non-flammable, non-toxic, and easy-to-remove byproduct carbon dioxide. Heterocyclic compounds are important backbones of various biologically active molecules, making research on new synthetic tactics for heterocyclic derivatives based on decarboxylative cyclization of great interest.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Applied
Sigrid Gavelle, Milan Innocent, Thomas Aubineau, Amandine Guerinot
Summary: This article provides an overview of recent advances in LMCT of carboxylates, with a special focus on mechanistic aspects of these transformations. Carboxylic acids can be considered as ideal biobased feedstocks in sustainable processes, and the photoinduced ligand-to-metal charge transfer offers low-consuming energy source and innovative conditions for mild and highly selective functionalization.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Ravindra B. Weerasooriya, Matthew C. Drummer, Brian T. Phelan, Jonathan L. Gesiorski, Emily A. Sprague-Klein, Lin X. Chen, Ksenija D. Glusac
Summary: This study reports the photochemical regeneration of benzoimidazole-based hydride donors using a phenazine-based metal-free chromophore, achieving a 50% hydride regeneration yield under optimal conditions. The proposed mechanism involves photoinduced electron transfer and proton transfer processes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Reina Nonami, Yu Kishino, Tomokazu Yamasaki, Kazuya Kanemoto, Kento Iwai, Nagatoshi Nishiwaki, Kazutaka Shibatomi, Tomohiko Shirai
Summary: We report the cationic Ir-catalyzed decarboxylation reactions that produce hydrocarbons in good yield (up to >99%) from various electron-rich and -poor aromatic carboxylic acids. This reaction is also applicable in decarboxylative hydroarylation of bicyclic alkenes and decarboxylative fluorination, indicating the potential utility of this catalytic decarboxylation in synthetic chemistry.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Fuli Deng, Juanjuan Huang, Erika E. Ember, Klaus Achterhold, Martin Dierolf, Andreas Jentys, Yue Liu, Franz Pfeiffer, Johannes A. Lercher
Summary: The study demonstrates that arylaliphatic acids can undergo decarboxylation on carbon-supported Pd nanoparticles with 100% selectivity at 90 degrees Celsius, and the reaction rate can be enhanced by preadsorbed hydrogen. The mechanism involves the dissociation of the α-C-H bond and the scission of C-COO.
Article
Chemistry, Multidisciplinary
Felix Glaser, Oliver S. Wenger
Summary: Combining the energy input from two red photons allows for chemical reactions that would normally require blue or ultraviolet irradiation. This biphotonic excitation strategy offers advantages such as deeper penetration and less photo-damage. By altering the photosensitizer in a dual photocatalytic system, the reaction outcome can be completely altered. Different biphotonic mechanisms lead to different photochemical reactivities, which can be controlled by changing the photosensitizer.
Article
Chemistry, Multidisciplinary
Stephan K. K. Pedersen, Sebastian Clementson, Kassem El-Chami, Jesper L. L. Kristensen, Mikkel Jessing
Summary: In this study, a decarboxylative alkenylation between alkyl carboxylic acids and enol triflates is reported, mediated by a dual catalytic nickel and iridium system under visible light irradiation. Two competing catalytic pathways involving the excited state iridium photocatalyst are identified. The desired electron transfer pathway leads to decarboxylation and the desired product, while the energy transfer pathway results in the formation of an undesired enol ester. The use of a highly oxidizing iridium photocatalyst is crucial for controlling the reactivity. The scope and limitations of the presented methodology are explored through the investigation of a diverse array of enol triflates and alkyl carboxylic acids.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Weibin Xie, Jiasheng Xu, Ubaidah Md Idros, Jouji Katsuhira, Masaaki Fuki, Masahiko Hayashi, Masahiro Yamanaka, Yasuhiro Kobori, Ryosuke Matsubara
Summary: Increasing levels of CO2 in the atmosphere is a pressing issue that needs to be addressed urgently to mitigate global temperature rise. A catalyst system that chemically reduces CO2 into useful compounds and meets certain criteria is necessary for global scale CO2RR. We propose a transition-metal-free catalyst system using an organohydride catalyst based on benzimidazoline for CO2RR, which can be regenerated using a carbazole photosensitizer and visible light, with promising results.
Article
Chemistry, Physical
Viet D. Nguyen, Ramon Trevino, Samuel G. Greco, Hadi D. Arman, Oleg V. Larionov
Summary: Dual catalytic systems involving photocatalytic activation and transition metal-catalyzed steps have enabled innovative approaches to the construction of carbon-carbon and carbon-heteroatom bonds. This study reports a dual catalytic process that enables the direct conversion of carboxylic acids to important synthetic intermediates using a three-component decarboxysulfonylative cross-coupling. Detailed mechanistic and computational studies revealed the roles of different catalysts and ions in channeling the reaction.
Article
Biochemistry & Molecular Biology
Ewelina Kowalska, Leslaw Sieron, Anna Albrecht
Summary: In this study, the synthesis of chiral hybrid pyrrolidine-chromanone polycyclic derivatives was described. A convenient (3+2)-annulation reaction of azomethine ylides with chromone-3-carboxylic acid under Bronsted base catalysis yielded highly functionalized products with good stereoselectivities through asymmetric, intermolecular, and decarboxylative (3+2)-cyclization.
Article
Chemistry, Physical
Kai Sun, Masato Ueno, Keisuke Imaeda, Kosei Ueno, Masaya Sawamura, Yohei Shimizu
Summary: A boron-catalyzed alpha-allylation of carboxylic acids with allylsulfones under blue LED irradiation conditions has been developed. The photoexcitation of catalytically generated boron enediolates induces single-electron transfer to the allylsulfones, leading to subsequent C-C bond formation and the construction of sterically demanding quaternary carbon centers at the position a to the carboxy group. The p-extended ligand on the boron atom is likely crucial for the efficient photoexcitation of the boron enediolates.
Article
Chemistry, Physical
Yasuharu Yoshimi
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2017)
Article
Polymer Science
Mugen Yamawaki, Akari Ukai, Yuki Kamiya, Shinji Sugihara, Miku Sakai, Yasuharu Yoshimi
Article
Chemistry, Multidisciplinary
Y. Iwata, Y. Tanaka, S. Kubosaki, T. Morita, Y. Yoshimi
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Organic
Takashi Yamamoto, Tomoya Iwasaki, Toshio Morita, Yasuharu Yoshimi
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Yosuke Tanaka, Suzuka Kubosaki, Kazuyuki Osaka, Mugen Yamawaki, Toshio Morita, Yasuharu Yoshimi
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Tomoya Iwasaki, Yuka Tajimi, Kenta Kameda, Callum Kingwell, William Wcislo, Kazuyuki Osaka, Mugen Yamawaki, Toshio Morita, Yasuharu Yoshimi
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Kazuyuki Osaka, Ayuka Usami, Tomoya Iwasaki, Mugen Yamawaki, Toshio Morita, Yasuharu Yoshimi
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Yui Ozaki, Tomoaki Yamada, Taisei Mizuno, Kazuyuki Osaka, Mugen Yamawaki, Hajime Maeda, Toshio Morita, Yasuharu Yoshimi
Article
Biochemistry & Molecular Biology
Mugen Yamawaki, Akiko Asano, Toshiki Furutani, Yuki Izumi, Yosuke Tanaka, Kazuyuki Osaka, Toshio Morita, Yasuharu Yoshimi
Article
Chemistry, Organic
Suzuka Kubosaki, Haruka Takeuchi, Yutaka Iwata, Yosuke Tanaka, Kazuyuki Osaka, Mugen Yamawaki, Toshio Morita, Yasuharu Yoshimi
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Yuka Tajimi, Yasuhiro Nachi, Ryoko Inada, Ryoga Hashimoto, Mugen Yamawaki, Kei Ohkubo, Toshio Morita, Yasuharu Yoshimi
Summary: Visible-light-induced decarboxylative and deboronative reactions were achieved using two-molecule organic photoredox catalysts. The high solubility improved reaction efficiency and product yield. The oxidation potential of the electron-donor molecule can be tuned for a wide range of substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yudai Shinkawa, Toshiki Furutani, Takumi Ikeda, Mugen Yamawaki, Toshio Morita, Yasuharu Yoshimi
Summary: The side-chain functionalization of aspartic/glutamic acid derivatives was achieved through photoinduced decarboxylation using organic two-molecule photoredox catalysts without racemization under mild conditions. A facile process involving the preparation of substrates and photoinduced decarboxylative radical additions provides easy access to the linked amino acids with carbohydrates and amino acids at the side chain.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mugen Yamawaki, Ryoga Hashimoto, Yuki Kawabata, Miwa Ichihashi, Yasuhiro Nachi, Rinpei Inari, Chisato Sakamoto, Toshio Morita, Yasuharu Yoshimi
Summary: In this study, visible-light-induced decarboxylative and deboronative radical addition of aliphatic carboxylic acids and arylboronic acid pinacol esters to electron-deficient alkenes was efficiently achieved using two-molecule organic photoredox catalysts. The reaction generated alkyl and aryl radicals to form radical adducts. The presence of a base and substrate played important roles in this photochemical system, and the sequential photoinduced decarboxylation of glutamic acid with two different carboxy groups was successfully carried out.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ryoga Hashimoto, Toshiki Furutani, Hirotsugu Suzuki, Yasuharu Yoshimi
Summary: In this study, the effects of electron-donors and counter-cations on the visible-light-induced deboronation and decarboxylation of arylboronic acid derivatives and benzoic acids were investigated using two-molecule photoredox catalysts. Different efficiencies in aryl radical generation were observed upon replacing the electron-donor and counter-cation. The rate of photoinduced deboronation of arylboronic acid derivatives strongly depends on the substituent, whereas the influence of counter-cation (Na* and K*) was relatively minor. In the case of the benzoate ion derived from benzoic acid, the effect of both substituent and counter-cation decreases because of the complex mechanism. Additionally, the dependence of the oxidation ability of the radical cation on the electron-donor suggests the possibility of roughly estimating the oxidation potentials of the arylborate and benzoate ions.
Article
Chemistry, Multidisciplinary
Yasuharu Yoshimi
Summary: Based on our recent results, this article explores the distinct reactivities of two-molecule photoredox systems compared to one-molecule photoredox systems. The inefficient electron transfer processes in the two-molecule system result in unique products through different pathways. The substitution of photoredox catalysts with appropriate oxidation/reduction potentials in this system provides valuable insights into photoredox reactions.
