Review
Chemistry, Organic
Sandeepan Maity
Summary: Samarium diiodide (SmI2) is a versatile single electron transfer reagent used in organic synthesis for stereoselective reactions. However, its stoichiometric usage poses environmental concerns limiting its broader applicability. Recent studies have focused on developing catalytic methods to rejuvenate the applications of SmI2 in synthetic organic chemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Nicholas D. C. Tappin, Philippe Renaud
Summary: An improved procedure for halogen atom and chalcogen group transfer radical additions is reported, utilizing the thermal decomposition of DTBHN to produce reactive methyl radicals. This initiation method generates gaseous or volatile byproducts for easy purification, with simple reaction conditions and broad scope of application demonstrated. Additionally, an alternative source of radicals, DTBPO, is also shown to be effective under identical conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Xiao-Xi Li, Xiaoyan Lu, Jae Woo Park, Kyung-Bin Cho, Wonwoo Nam
Summary: High-valent iron-imido complexes have multiple energetically close-lying electromers and can perform efficient oxidations, unlike common iron-oxo species. The reactivity of these complexes can emulate multi-spin state reactions, and a new non-rebound mechanism is proposed for C-H activation reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ludivine Delfau, Samantha Nichilo, Florian Molton, Julie Broggi, Eder Tomas-Mendivil, David Martin
Summary: This study reported the synthesis of acyl azolium salts from various types of carbenes and the generation of their corresponding radicals and enolates, revealing the role of additives in the redox behavior of these compounds and correcting misconceptions about radical transformations of aldehyde derivatives. The reducing ability of enolates derived from certain carbenes was found to be underestimated, and catalytic intermediates were shown to transfer electrons efficiently at room temperature. Enol derivatives of certain carbenes were identified as powerful reducing agents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Biochemistry & Molecular Biology
Marina A. Tzani, Dimitra K. Gioftsidou, Michael G. Kallitsakis, Nikolaos V. Pliatsios, Natasa P. Kalogiouri, Panagiotis A. Angaridis, Ioannis N. Lykakis, Michael A. Terzidis
Summary: This review explores the mechanisms and applications of chemiluminescence, including both direct and indirect production modes. It discusses the characteristics of chemical reactions and CL mechanisms, summarizes methods to enhance CL efficiency, and examines the role of CL in the development of therapeutic platforms.
Review
Crystallography
Weiqing She, Zhenzhen Xu, Lianjie Zhai, Junlin Zhang, Jie Huang, Weiqiang Pang, Bozhou Wang
Summary: Due to the introduction of oxygen atoms, N-oxide energetic compounds possess unique advantages in terms of oxygen balance, detonation properties, and energy density, which have attracted extensive attention from researchers worldwide. This article provides a comprehensive review of the synthetic strategies for two categories of N-oxides, azine N-oxides and azole N-oxides, and discusses the reaction mechanisms of aromatic N-oxide frameworks and their applications in creating high-energy substances. Furthermore, the energetic properties of N-oxide energetic compounds are compared and summarized.
Review
Acoustics
Ingrid V. Machado, Jhonathan R. N. dos Santos, Marcelo A. P. Januario, Arlene G. Correa
Summary: By utilizing ultrasound-assisted multicomponent reactions under heterogeneous catalysis, it is possible to efficiently synthesize biologically active organic compounds with reduced costs and energy consumption.
ULTRASONICS SONOCHEMISTRY
(2021)
Article
Engineering, Environmental
Jinxing Zhang, Zhaoyu Zhou, Zhiyuan Feng, Hongying Zhao, Guohua Zhao
Summary: This study proposes a strategy for the fast generation of hydroxyl radicals through rerouting the electron transfer pathway. By modifying F-TiO2, the electrocatalytic reduction of oxygen to H2O2 with high selectivity is achieved, and an additional channel facilitates the generation of hydroxyl radicals. The proposed method shows fast kinetics for removing organic pollutants in wastewater treatment, and the degradation efficiency is less affected by the water source and pH value.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Organic
Kenta Tanaka, Mami Kishimoto, Yuta Tanaka, Yusuke Kamiyama, Yosuke Asada, Mayumi Sukekawa, Naoya Ohtsuka, Toshiyasu Suzuki, Norie Momiyama, Kiyoshi Honda, Yujiro Hoshino
Summary: New moderately oxidizing thioxanthylium photoredox catalysts have been developed that can efficiently promote radical-cation Diels-Alder reactions under green light irradiation. These catalysts have relatively moderate excited-state reduction potentials and can tolerate beta-halogenostyrenes, producing synthetically useful halocyclohexenes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Wanyi Liao, Qin Zhao, Shanshan Wang, Yiling Ran, Hong Su, Rong Gan, Shun Lu, Yan Zhang
Summary: The high energy consumption in water electrolysis systems is attributed to the slow kinetics of the oxygen evolution reaction (OER). Substituting thermodynamically advantageous small molecule oxidation reactions for OER can significantly improve energy conversion efficiency. Studying the in-depth reaction mechanism of complex substrates is necessary due to their elemental composition. This review focuses on the electrooxidation mechanism of different substrate molecules, such as ethanol, urea, and hydrazine, and introduces design ideas and strategies for high-performance electrocatalysts in relation to reaction path selectivity. The challenges in achieving industrial transformation in this field are also discussed.
JOURNAL OF CATALYSIS
(2023)
Review
Nanoscience & Nanotechnology
Hongliang Chen, Chuancheng Jia, Xin Zhu, Chen Yang, Xuefeng Guo, J. Fraser Stoddart
Summary: Developing new materials is a long-standing goal in various fields, and understanding single-molecule reactions can deepen our understanding of chemical reactions and provide new frameworks in materials science. This review focuses on state-of-the-art chemical reactions in single-molecule junctions and highlights the advantages of real-time testbeds for studying reaction dynamics, intermediates, transition states, and solvent effects. The behavior of single-molecule reactions is compared with reactions in ensemble states, and the potential of leveraging single-molecule catalysis for large-scale materials production is explored.
NATURE REVIEWS MATERIALS
(2023)
Review
Chemistry, Applied
Shivani Sharma, Jitender Singh, Anuj Sharma
Summary: The novel concept of radical-polar crossover (RPCO) and polar-radical crossover (PRCO) reactions has emerged in recent years as a valuable tool bridging the gap between polar and radical reactions, overcoming their limitations, and improving the green quotient of reactions. The development and transformation of this area into synthetically important reactions is summarized in this review.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Environmental Sciences
Shuying Qiu, Yan Wang, Jinquan Wan, Yongwen Ma, Zhicheng Yan, Shou Yang
Summary: This study demonstrated the efficient removal of sulfamethoxazole using Ce/Fe-nanoporous carbon modified graphite felt electrode in a heterogeneous electro-Fenton system, highlighting the enhanced electrocatalytic activity with Ce doping. The mesoporous Ce/Fe@NPC-GF cathode showed high oxygen reduction activity, low resistance, and remarkable interfacial electron transfer, leading to in-situ H2O2 generation and production of reactive radicals. The electrode exhibited high stability and outstanding catalytic capacity even after 8 cycles, emphasizing its potential as an efficient heterogeneous electro-Fenton cathode material.
Article
Chemistry, Physical
Kuohong Chen, Jiaming Zhang, Qianqian Shi, Lili Han, Dongmin Fu, Donghui Wei, Yanyan Zhu
Summary: Understanding the mechanisms and origin of regio- and stereoselectivities in N-heterocyclic carbene (NHC)-catalyzed radical reactions of enals and pyridinium salts remains a significant challenge in radical chemistry. This study used density functional theory calculations to explore the possible mechanisms and the factors controlling selectivities. The findings shed light on the detailed steps involved in these reactions and provide valuable insight for theoretical investigations on radical reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Takashi Koike, Ryo Okumura, Tomoki Kato, Manabu Abe, Munetaka Akita
Summary: In this study, a method for photocatalytic generation of alkyl radicals from readily accessible alkyl benzoate esters is described. The excited organic photocatalyst, 1,4-bis(diphenylamino)benzene (BDB), acts as a one-electron injector. The hydroxy-1,1-dialkylfluoroethylation of aromatic alkenes is achieved using this photoredox-catalytic system. Furthermore, a strategy for generating fluoroalkyl radicals from readily available 2-fluorinated 1,1-dialkylethanols is developed.
Article
Chemistry, Organic
Shigenobu Umemiya, Yujiro Hayashi
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2015)
Article
Chemistry, Multidisciplinary
Yu Feng, Dane Holte, Jochen Zoller, Shigenobu Umemiya, Leah R. Simke, Phil S. Baran
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2015)
Article
Chemistry, Multidisciplinary
Luisruben P. Martinez, Shigenobu Umemiya, Sarah E. Wengryniuk, Phil S. Baran
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Organic
Shigenobu Umemiya, Daisuke Sakamoto, Genki Kawauchi, Yujiro Hayashi
Article
Chemistry, Multidisciplinary
Genki Kawauchi, Shigenobu Umemiya, Tohru Taniguchi, Kenji Monde, Yujiro Hayashi
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Chemistry, Organic
Yujiro Hayashi, Kaito Nagai, Shigenobu Umemiya
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Yujiro Hayashi, Tomoaki Yamada, Misaki Sato, Shoya Watanabe, Eunsang Kwon, Kotaro Iwasaki, Shigenobu Umemiya
Article
Chemistry, Multidisciplinary
Yujiro Hayashi, Kaito Nagai, Shigenobu Umemiya
CHEMISTRY-AN ASIAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Seitaro Koshino, Akira Takikawa, Keiichi Ishida, Tohru Taniguchi, Kenji Monde, Eunsang Kwon, Shigenobu Umemiya, Yujiro Hayashi
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Jun Kikuchi, Kyohei Takano, Yusuke Ota, Shigenobu Umemiya, Masahiro Terada
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Yuzuru Kanda, Hugh Nakamura, Shigenobu Umemiya, Ravi Kumar Puthukanoori, Venkata Ramana Murthy Appala, Gopi Krishna Gaddamanugu, Bheema Rao Paraselli, Phil S. Baran
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Shigenobu Umemiya, Masahiro Terade
Summary: An enantioselective allylation of silyl-substituted acetylenic aldehydes was developed using chiral phosphoric acid/transition metal cooperative catalysis, yielding enantioenriched homoallylic propargyl alcohols with high yields and excellent enantioselectivities. This method also enabled the shortest formal synthesis of fostriecin, achieving the known intermediate in only nine steps with a total yield of 39%.
Correction
Chemistry, Physical
Satavisha Kayal, Jun Kikuchi, Masahiro Shimizu, Naoya Shinagawa, Shigenobu Umemiya, Masahiro Terada
Article
Chemistry, Organic
Shigenobu Umemiya, Naoya Shinagawa, Masahiro Terada
Summary: A scalable total synthesis of leucascandrolide A macrolactone has been achieved in 17 steps with a longest linear sequence and a yield of 31.2% from readily available feedstocks. The key steps in this synthesis include enantioselective allylation reaction using chiral phosphoric acid (CPA)/CuBr cooperative catalysis and diastereoselective catalytic crotylation in the presence of CPA with CuCl. These catalytic reactions can be performed on a gram scale and result in excellent stereoselectivities.
Article
Chemistry, Multidisciplinary
Satavisha Kayal, Jun Kikuchi, Naoya Shinagawa, Shigenobu Umemiya, Masahiro Terada
Summary: This study achieved a highly efficient and enantioselective reaction through the use of a co-catalyst system, resulting in enantioenriched compounds and the recovery of the starting material. It provides a new synthetic method for the synthesis of multifunctional compounds.