Article
Chemistry, Organic
Bin Sun, Rui Zhu, Xiaohui Zhuang, Xiayue Shi, Panyi Huang, Zhiyang Yan, Chuanming Yu, Can Jin
Summary: This efficient and novel method involves regioselective hydroxydifluoroacetamidation of alkenes with bromodifluoroacetamides through a tandem radical pathway mediated by photoredox catalysis under metal-free conditions. The reaction, using Rhodamine 6G as the photocatalyst, produces a series of alpha,alpha-difluoro-gamma-hydroxyacetamides in moderate to excellent yields, demonstrating the advantages of low-cost photocatalyst, readily available starting materials, synthetic convenience, and wide functional group compatibility.
Article
Chemistry, Organic
Zengqiang Feng, Baoxiang Zhu, Bingbing Dong, Li Cheng, Yunpu Li, Zechao Wang, Junliang Wu
Summary: An efficient and novel visible-light-promoted radical difluoromethylation method for synthesizing alpha-CF2H-substituted ketones has been described in this study. Various alpha-CF2H-substituted ketones are successfully created based on a SET process, providing a simple and operationally straightforward method with broad functional group compatibility.
Article
Chemistry, Applied
Tomer M. Faraggi, Caroline Rouget-Virbel, Juan A. Rincon, Mario Barberis, Carlos Mateos, Susana Garcia-Cerrada, Javier Agejas, Oscar de Frutos, David W. C. MacMillan
Summary: The conversion of serine to optically pure unnatural amino acids can be achieved through a two-step process utilizing a photocatalytic cross-electrophile coupling. This method produces artificial analogues of phenylalanine, tryptophan, and histidine, and is tolerant of a broad range of functionalities. It can also be leveraged for the scalable synthesis of valuable pharmaceutical scaffolds via flow technology.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Organic
Yongxiang Zheng, Anna Perfetto, Davide Luise, Ilaria Ciofini, Laurence Miesch
Summary: The research demonstrates the use of difluorinated diazoacetone as a practical reagent for the direct synthesis of CF2H-substituted 2-amidofurans. These newly designed amidofurans were further developed to create new nitrogen-containing frameworks that may be challenging to obtain otherwise.
Article
Chemistry, Organic
Bei Zhang, Jian Wang
Summary: In this study, a new acyldifluoromethylation reaction has been reported, which achieves efficient synthesis on inert alkenes through synergistic catalysis. The method exhibits a broad substrate scope and good functional group tolerance.
Article
Chemistry, Organic
Rui Li, Chen-Xi Yang, Bai-Hua Niu, Li-Juan Li, Ji-Mei Ma, Zi-Long Li, Hong Jiang, Wan-Min Cheng
Summary: A highly efficient photoinduced nickel-catalyzed method for the C-heteroatom cross-coupling of aryl halides is reported. This method does not require external photosensitizers and can successfully couple various nucleophiles with electronically diverse aryl halides, providing a universal approach for different C-heteroatom coupling reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Arghya Banerjee, Satavisha Sarkar, Jagrut A. Shah, Nicoline C. Frederiks, Emmanuel A. Bazan-Bergamino, Christopher J. Johnson, Ming-Yu Ngai
Summary: The study presents a visible-light-induced copper catalysis for the production of diverse heterocycles, with high tolerance to various functional groups. Preliminary mechanistic investigation suggests a cooperative action of two catalysts under visible-light irradiation to facilitate the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shiwei Pan, Fan Chen, Yanyan Zhang, Liang Shao, Lingling Chu
Summary: A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF2H via nickel catalysis is reported. This method involves migratory insertion of nickel hydride to alkyne followed by CF2H-coupling, giving access to various branched CF2H-alkenes with high efficiency and exclusive regioselectivity. The mild conditions used are compatible with a wide range of aliphatic and aryl alkynes, making it a versatile and promising approach. Mechanistic studies have been conducted to support the proposed reaction pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xian Zhao, Xiaoliang Feng, Fan Chen, Shengqing Zhu, Feng-Ling Qing, Lingling Chu
Summary: A metallaphotoredox-catalyzed strategy for the aminocarbonylation of alkynes with amines and CO has been developed. This method allows for selective synthesis of alpha,beta-unsaturated amides and a sequential four-component hydroaminocarbonylation/radical alkylation, demonstrating great potential in the selective and divergent functionalization of alkynes. Preliminary mechanistic studies suggest a photoinduced oxidative insertion of aniline and CO into nickel followed by a migratory insertion of (carbamoyl)nickel species may be involved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Zhe Dong, David W. C. MacMillan
Summary: Metal-catalysed cross-couplings are widely used for the formation of C-C bonds, but alkyl cross-couplings using alcohols as coupling partners remain relatively underdeveloped. A new method for direct deoxygenative cross-coupling of free alcohols has been developed, showing potential for a wide range of applications, including the pharmaceutical industry. This technology represents a general strategy for combining in situ alcohol activation with transition metal catalysis.
Article
Chemistry, Applied
Lilian Geniller, Marc Taillefer, Florian Jaroschik, Alexis Prieto
Summary: The Ni-photoredox catalyzed desulfurative cross-coupling reaction enables the synthesis of various unsymmetrical diarylmethane molecules under mild reaction conditions, providing new transformations of abundant, naturally occurring thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Scott T. Shreiber, David A. Vicic
Summary: The solvated nickel complexes react with organic electrophiles to synthesize fluoroalkylated organic products. Electrochemical analysis reveals that nickel complexes can act as reservoirs of CF3 groups under certain conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Heng Jiang, Xiaoye Yu, Constantin G. Daniliuc, Armido Studer
Summary: A three-component 1,2-aminoarylation reaction is reported, utilizing synergistic photoredox and nickel catalysis. The method shows high functional group tolerance and broad substrate scope, allowing for the stereoselective synthesis of enantiopure alpha-arylated beta-amino alcohols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Min Zhang, Qiang Li, Jin-Hong Lin, Ji-Chang Xiao
Summary: Due to its unique electronic properties, the difluoromethylene group (CF2) has been used in the design of biologically active molecules. The synthesis of alpha,alpha-difluoro-gamma-lactones has gained attention due to their potential unexpected biological activities. Traditional synthetic methods are tedious, but a new method using BrCF2CO2K under photoredox catalysis has been developed, which is efficient and atom economy.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Yantao Li, Qianzhen Shao, Hengchi He, Chengjian Zhu, Xiao-Song Xue, Jin Xie
Summary: The authors present a method to synthesize tetrasubstituted olefins via dual photo- and nickel catalysis under an air atmosphere, without the need for an inert atmosphere. The synthesis of these compounds under mild conditions is challenging, but the authors were able to achieve it by using readily available carboxylic acids and alkenyl triflates. The method shows promise for applications in complex molecule modification and gram-scale synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Masaru Kondo, Kento Nakamura, Chandu G. Krishnan, Shinobu Takizawa, Tsukasa Abe, Hiroaki Sasai
Summary: The Azo-crown ether-based photoswitching chiral phase transfer catalysts control catalytic activity through structural transformation induced by E/Z photoisomerization. This allows for promotion or hindrance of the enantioselective alkylation of glycine Schiff base to yield chiral amino acid derivatives.
Article
Chemistry, Multidisciplinary
Andres Arribas, Martin Calvelo, David F. Fernandez, Catarina A. B. Rodrigues, Jose L. Mascarenas, Fernando Lopez
Summary: The study presents a versatile and highly enantioselective intramolecular hydrocarbonation reaction for the synthesis of heteropolycyclic systems with chiral quaternary carbon stereocenters. The method relies on an iridium-(I)/bisphosphine chiral catalyst, yielding fused indole and pyrrole products with high enantiomeric excesses. DFT computational studies provided a detailed mechanistic profile and identified weak non-covalent interactions as key factors controlling the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Eisuke Sato, Mayu Fujii, Hiroki Tanaka, Koichi Mitsudo, Masaru Kondo, Shinobu Takizawa, Hiroaki Sasai, Takeshi Washio, Kazunori Ishikawa, Seiji Suga
Summary: This paper presents an electrochemically initiated cyanosilylation of carbonyl compounds, with machine learning-assisted optimization to determine the best productivity conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuki Naito, Masaru Kondo, Yuto Nakamura, Naoki Shida, Kazunori Ishikawa, Takashi Washio, Shinobu Takizawa, Mahito Atobe
Summary: This study performed multiparameter screening of reductive carboxylation in an electrochemical flow microreactor using a Bayesian optimization strategy. The developed algorithm constrained the passed charge for the electrochemical reaction, leading to the instantaneous discovery of suitable conditions for the desired reaction. Analysis of the suggested conditions by the Bayesian optimization underscored their physicochemical validity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Chandu G. Krishnan, Masaru Kondo, Kento Nakamura, Hiroaki Sasai, Shinobu Takizawa
Summary: Design of a suitable photoswitchable chiral cation-binding cage for the synthesis of optically active aminals was established through E/Z isomerization, resulting in enhanced catalytic activity and enantioselectivity.
Article
Multidisciplinary Sciences
James Oakley, Benito F. Buksh, David F. Fernandez, Daniel G. Oblinsky, Ciaran P. Seath, Jacob B. Geri, Gregory D. Scholes, David W. C. MacMillan
Summary: The elucidation of protein interaction networks is critical to understanding biology and developing therapeutics. Proximity labeling platforms (PLPs) are advanced technologies that can discover and describe biomolecular networks by tagging protein-protein interactions. By expanding the labeling resolution of PLPs, it is possible to capture interactions at different size scales more effectively.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Saori Suzuki, Jacob B. Geri, Steve D. Knutson, Harris Bell-Temin, Tomokazu Tamura, David F. Fernandez, Gabrielle H. Lovett, Nicholas A. Till, Brigitte L. Heller, Jinchao Guo, David W. C. MacMillan, Alexander Ploss
Summary: This study used mu Map to analyze the spike interactome of SARS-CoV-2 and identified eight novel candidate receptors. Experimental validation showed that co-expression of ACE2 with other receptors significantly enhances viral uptake.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Masaru Kondo, Kento Nakamura, Chandu G. Krishnan, Hiroaki Sasai, Shinobu Takizawa
Summary: This study presents recent advances in photoswitchable chiral organocatalysts and their applications in the photomodulation of enantioselective reactions. Under appropriate light irradiation, the E/Z-photoisomerization of the photoresponsive units on the catalysts controls the catalytic activity and/or selectivity of the reactions. The study also elucidates the design, synthesis, and catalytic application of azobenzene BINOL-based photoswitchable chiral phase-transfer catalysts. This account provides insights into the appropriate design of a photoswitchable chiral organocatalyst for achieving good enantioselectivity and photocontrol.
Article
Chemistry, Organic
David F. Fernandez, Maria Gonzalez-Esguevillas, Sebastian Keess, Felix Schafer, Jens Mohr, Andre Shavnya, Thomas Knauber, David C. Blakemore, David W. C. MacMillan
Summary: We present a general approach to synthesis of diversified libraries featuring aliphatic core rings via photoredox catalysis under mild conditions.
Article
Chemistry, Multidisciplinary
Chandu G. Krishnan, Masaru Kondo, Osamu Yasuda, Duona Fan, Kento Nakamura, Yoshitomo Wakabayashi, Hiroaki Sasai, Shinobu Takizawa
Summary: Bis(dithienylethene)-based BINOL-derived phosphoric acid (DTE-BPA) has been developed as a light-controlled chiral organocatalyst for the first time. The photoinduced modulation of the reactivity and selectivity via the open/close isomerization of the DTE scaffold led to superior light-controlled ability in the enantioselective aza-Friedel-Crafts reaction of aldimines with indoles. DFT studies showed that photoisomerization is accompanied by a shift of 1.1 pK(a) units between the open and closed isomers.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Masaru Kondo, Tatsuya Joutsuka, Kakeru Fujiwara, Tetsuo Honma, Masahiko Nishijima, Shohei Tada
Summary: In this study, we investigated the Chan-Lam cross-coupling of imidazole and arylboronic acids using heterogeneous CuO/MOX catalysts under additive-free and mild conditions. Among them, CuO/t-ZrO2 showed the best performance, with a turnover number more than ten times higher than that of bulk CuO. Experimental and computational approaches revealed that the surface structure of CuO/t-ZrO2 contained abundant highly reducible Cu2+ species, specifically square-planar [CuO4], which played a crucial role in the coupling reaction.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Vlad Bacauanu, Zoe N. Merz, Zhong L. Hua, Simon B. Lang
Summary: This article describes a new biocompatible method for post-translational protein modification, which is crucial for improving chemical probes and biologic therapies. By utilizing a specific chemical reaction, aromatic compounds can be linked to cysteine residues on peptides and proteins for the preparation of ADCs. The application of this method in drug discovery is highlighted, demonstrating the construction of novel ADCs with target-mediated in vitro cytotoxic activity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Yasukazu Kobayashi, Shohei Tada, Masaru Kondo, Kakeru Fujiwara, Hiroshi Mizoguchi
Summary: Intermetallic YIr2 nanoparticles with a high surface area were prepared and found to possess high catalytic activity for the hydrogenation of cyclohexanone to cyclohexanol. This unique activity can be attributed to the charge transfer from Y to Ir, as supported by density functional theory calculations.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Masaru Kondo, Tomohiro Agou
Summary: In this study, DBAB was used as a photocatalyst for the aerobic photooxidation of triarylphosphines, leading to the formation of phosphine oxides in moderate yields. The results highlight the potential application of DBAB in photocatalysis.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yasukazu Kobayashi, Shohei Tada, Masaru Kondo, Kakeru Fujiwara, Hiroshi Mizoguchi
Summary: Intermetallic CaPt2 nanoparticles, prepared using a molten salt method, exhibited superior catalytic activity compared to a commercial Pt/C catalyst in the hydrogenation of ketones to alcohols, which could be attributed to electron-rich Pt sites in CaPt2.
CHEMICAL COMMUNICATIONS
(2022)
