Article
Chemistry, Organic
Olga M. Mulina, Alexey I. Ilovaisky, Till Opatz, Alexander O. Terent'ev
Summary: A metal-free visible light photoredox-catalyzed synthesis of N-unsubstituted enaminosulfones from vinyl azides and sodium sulfinates in moderate to high yields. The process shows impressive selectivity and involves multiple steps.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Thomas Abegg, Janine Cossy, Christophe Meyer
Summary: cis-1,2-Dialkenylcyclopropanes with a vinyl azide group were generated by Knoevenagel condensations and underwent cascade Cope and Winstein [3,3]-sigmatropic rearrangements under mild conditions. This reaction sequence allows for the synthesis of diversely substituted 1,4-cycloheptadienes with a secondary allylic azide containing up to three stereocenters.
Article
Biochemistry & Molecular Biology
Vera A. Vil, Sergei S. Grishin, Alexander O. Terent'ev
Summary: An electrochemical method for synthesizing imidazoles has been developed, resulting in a wide range of products with high yields. The process involves multiple steps, including the generation of electrophilic iodine species, the formation of 2H-azirine from vinyl azide, and the reactions with benzyl amine and imine generated from benzyl amine. Despite the potential reduction of unsaturated intermediates with C=N bonds, the synthesis of imidazoles proceeds efficiently.
Article
Chemistry, Organic
Li-Ming Zhang, Li-Rong Wen, Xiao-Dong Niu, Wei-Si Guo, Ming Li
Summary: An efficient protocol for synthesizing thiophene derivatives from b-ketothioamides and vinyl azides using InCl3 as a catalyst was developed. This new procedure offers the advantages of simple operation and wide tolerance of functional groups, providing an interesting method for accessing thiophene derivatives.
Article
Chemistry, Multidisciplinary
Deli Sun, Xianghua Tao, Guobin Ma, Jifen Wang, Yunrong Chen
Summary: We report an asymmetric Ni-catalyzed cross-electrophile coupling approach for the preparation of enantioenriched aryl/vinyl alkyl carbinol esters. The method demonstrates a broad substrate scope and tolerance towards various functional groups.
Article
Chemistry, Multidisciplinary
Qi Liang, Long Lin, Guodong Li, Xianqiang Kong, Bo Xu
Summary: A copper-catalyzed radical cyclization method was developed for the synthesis of cyanoalkyl-substituted phenanthridines and quinoxalines, showing excellent isolated yields. The reactions proceed under mild conditions, exhibit a broad substrate scope, and have excellent functional group tolerance.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Shanshan Shi, Hu Chen, Ming Zhao, Shiwei Yang, Pan Li, Xiaohong Wang, Jinmiao Zhu, Qi Fang, Wenbiao Xu, Guo Tang, Yuzhen Gao
Summary: A convenient copper-catalyzed reaction has been developed for the synthesis of a variety of (E)-beta-fluoroalkyl vinyl phosphorothioates with excellent regioselectivity and stereoselectivity. This method features mild reaction conditions, simple operation, good functional group tolerance, and late-stage functionalization of bioactive molecules.
Article
Chemistry, Organic
Nuria Vazquez-Galinanes, Isabel Velo-Heleno, Martin Fananas-Mastral
Summary: A method for the use of vinyl epoxides in catalytic allylboration of alkynes is described, which allows for the synthesis of bifunctional skipped dienes bearing both an allylic alcohol and an alkenylboronate from simple starting materials with high regio- and stereoselectivity. These products show versatile reactivity and can be converted into cyclic boron compounds and polyenes.
Article
Chemistry, Organic
Akanksha M. Pandey, Shankhajit Mondal, Boopathy Gnanaprakasam
Summary: Continuous-flow reactors are an ideal tool for synthesizing potentially explosive but synthetically useful organic substances. This study reports the continuous-flow direct azidation of alcohols using TMSN3 as a transfer reagent and Amberlyst-15 as a recyclable catalyst. The study also explores the application of continuous-flow reactors in other organic reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Li -Ming Zhang, Li-Rong Wen, Xing Xin, Ming Li
Summary: A rapid and facile method for synthesizing diverse thiophene derivatives was developed via cyclization of b-oxodithioesters and vinyl azides. This method is highly efficient, resulting in moderate to good yields of diverse b-oxodithioesters and vinyl azides.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Applied
Brian Spiegelberg, Haijun Jiao, Reni Grauke, Christoph Kubis, Anke Spannenberg, Adrian Brandt, Andreas Taden, Horst Beck, Sergey Tin, Johannes G. Vries
Summary: The study achieved the iridium-catalyzed transfer vinylation of bio-based polyols and other alcohols and phenols using vinyl acetate in a green solvent. The optimized synthetic procedure demonstrated high selectivity by suppressing side reactions efficiently, leading to the formation of bis-vinyl ethers.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Stanislav A. Paveliev, Oleg O. Segida, Olga M. Mulina, Igor B. Krylov, Alexander O. Terent'ev
Summary: A visible light-induced synthesis of enaminones from vinyl azides and aldehydes using decatungstate photocatalysis has been developed. The reaction proceeds through several steps, resulting in the desired products with good yield.
Article
Multidisciplinary Sciences
Xuelun Duan, Nan Zheng, Ming Li, Gongbo Liu, Xinhao Sun, Qiming Wu, Wangze Song
Summary: The discovery and study of new fundamental intermediates composed of carbon and nitrogen is crucial in organic chemistry. The authors reported the formation of alkylidene ketenimine through a copper-catalyzed three-component reaction under mild conditions. This reaction involves cycloaddition, nitrogen extrusion, and carbene-assisted rearrangement, and exhibits excellent selectivity and stereospecificity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Dinesh Kumar Gopalakrishnan, Sourav Panigrahi, Raju Sen, Janakiram Vaitla
Summary: A method has been developed for the synthesis of allyl substituted gamma-butenolides through carbonyl ylide rearrangement. The reaction proceeds via a carbonyl ylide generation/allyloxy furan formation/[3,3]-sigmatropic rearrangement/isomerization sequence to form 3-allyl butenolides at room temperature. At 70 degrees Celsius, the resulting [3,3]-sigmatropic rearrangement product further undergoes [3,3]-sigmatropic rearrangement to produce 5-allyl butenolide. Without a catalyst, the reaction leads to a diene via [2,3]-sigmatropic rearrangement.
Article
Chemistry, Organic
Wei Wu, Shunli Wen, Xinyu Zhang, Qi Lin, Zhiqiang Weng
Summary: A highly efficient and regioselective synthesis of highly substituted 2-trifluoromethyl pyrrole derivatives is reported via a silver-catalyzed cyclization of vinyl azides with ethyl 4,4,4-trifluoro-3-oxobutanoate. Various types of alpha-(heteo)aryl, alkyl, alpha-aryl, and alpha,beta-disubstituted vinyl azides can participate in this transformation. The proposed reaction mechanism involves the addition of in situ generated 2H-azirine to the diketone species, followed by intramolecular addition, N-C-1 cleavage, and elimination.
Article
Chemistry, Multidisciplinary
Bin Wang, Yihang Li, Jia Hao Pang, Kohei Watanabe, Ryo Takita, Shunsuke Chiba
Summary: A protocol for regio-controlled hydromagnesiation of 1,3-enynes was developed using magnesium hydride generated in situ by solvothermal treatment of sodium hydride and magnesium iodide in THF. The resulting allenylmagnesium species could be converted into tri- and tetra-substituted allenes by subsequent treatment with various carbon- and silicon-based electrophiles with the aid of CuCN as a catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Haoyu Li, Xinxin Tang, Jia Hao Pang, Xiangyang Wu, Edwin K. L. Yeow, Jie Wu, Shunsuke Chiba
Summary: This study reveals the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. By photoexcitation of tetrasulfide dianions, single-electron reduction of aryl halides is achieved, leading to the participation of aryl radicals in cross-coupling, borylation, and hydrogenation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuliang Liu, Haoyu Li, Shunsuke Chiba
Summary: A protocol for photoinduced cross-coupling of aryl iodides and alkenes has been developed, utilizing a radical cascade mechanism. This method enables selective coupling of iodides over other halogen leaving groups and is compatible with various functional groups on both arene and alkene motifs.
Article
Chemistry, Medicinal
Xudong Cao, Peng Wang, Haoxing Yuan, Haoran Zhang, Yan He, Kequan Fu, Qian Fang, Hongli Liu, Limin Su, Long Yin, Pei Xu, Yuyang Xie, Xiaochun Xiong, Junqi Wang, Xu Zhu, Dong Guo
Summary: Compound 25 holds therapeutic potential for the treatment of ADPKD by inhibiting cyst formation and growth through the suppression of cAMP activity on V2R.
JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Pei Xu, Xing-Yu Wang, Zhijuan Wang, Jinjin Zhao, Xu-Dong Cao, Xiao-Chun Xiong, Yu-Chao Yuan, Songlei Zhu, Dong Guo, Xu Zhu
Summary: This article describes a catalytic strategy for the direct alkylation of trifluoromethylbenzimidazoles at the single C(sp(3))-F bond using a photoinduced thiol catalysis process. The CO2 radical anion (CO2 center dot-) has been identified as the most efficient single-electron reductant for achieving this transformation. The spin-center shift of the generated radical anion intermediate plays a key role in the mild and efficient activation of the C-F bond.
Article
Chemistry, Organic
Jiahua Chen, Jun Wei Lim, Shunsuke Chiba
Summary: An facile method for the conversion of 2-piperidones and 2-pyrrolidones into 2-cyano-3-iodo piperidines or pyrrolidines has been achieved through a sequence of controlled hydride reduction, silylation, iodination, and cyanation, resulting in high diastereoselectivity and good yields.
Article
Chemistry, Multidisciplinary
Yihang Li, Jiahua Chen, Jaslyn Jing Wen Ng, Shunsuke Chiba
Summary: A protocol was developed to generate allylmagnesium reagents from 2-aryl-1,3-dienes using in situ generated magnesium hydride (MgH2) through solvothermal treatment of sodium hydride (NaH) and magnesium iodide (MgI2) in tetrahydrofuran (THF). Downstream functionalization of the resulting allylmagnesium reagents with carbonyl compounds or alkyl (pseudo)halides led to branched products with an allylic quaternary carbon center, while reaction with chlorosilanes resulted in regio and stereoselective formation of linear allylsilanes. Further derivatizations of the homoallylic alcohols and allylsilanes were also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Eugene Yew Kun Tan, Amirah S. Mat Lani, Wayne Sow, Yuliang Liu, Haoyu Li, Shunsuke Chiba
Summary: The facile construction of C(sp(3))-rich carbo- and heterocyclic compounds is an important synthetic strategy for contemporary drug discovery programs. In the presence of potassium formate and methanol under visible light irradiation, polysulfide anions can catalyze the dearomatization process of substituted naphthalenes, indoles, and other related heteroaromatic compounds. This method demonstrates broad functional group tolerance, operational simplicity, scalability, and cost-effectiveness, making it a practical and sustainable synthetic tool for arene dearomatization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Itziar Guerrero, Eugene Yew Kun Tan, Yuliang Liu, Lee J. Edwards, Shunsuke Chiba
Summary: A photochemical protocol has been developed for the alkylation of diazines (pyrimidines, pyrazines, and pyridazines) with N-(acyloxy)phthalimides. The process is facilitated by the presence of triethylamine under irradiation with 427-390 nm light, enabling rapid cross-coupling reactions to construct a wide range of alkylated diazines.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Eugene Yew Kun Tan, Amirah S. Mat Lani, Wayne Sow, Yuliang Liu, Haoyu Li, Shunsuke Chiba
Summary: The study demonstrates a method using polysulfide anions to catalyze the dearomatization process under visible light irradiation. The developed protocol exhibits broad functional group tolerance, operational simplicity, scalability, and cost-effectiveness, making it a practical synthetic tool.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yi Zhen Tan, Xiangyang Wu, Yunpeng Lu, Shunsuke Chiba, Edwin K. L. Yeow
Summary: In this study, the researchers found that the heteroleptic Ir(iii) complex 1, combined with N-(tert-butoxycarbonyl)-proline and cesium carbonate, can facilitate the hydrodehalogenation of reductively inert aryl halides under blue light irradiation. The in situ modified Ir-int structure leads to a bathochromic shift of excited triplet state absorption and phosphorescence bands. Free Ir-int ions are responsible for the hydrodehalogenation reaction of aryl halides.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Haoyu Li, Shunsuke Chiba
Summary: A photocatalytic method using polysulfide anions as catalysts enables the synthesis of alpha-tertiary amines through alpha-C-H functionalization of a-secondary benzylamines with cyanoarenes or aryl ketones. The key factors include the highly negative oxidation potential of polysulfide dianions and the catenated structure of polysulfide anion radicals, facilitating the construction of sterically congested alpha-tertiary amine scaffolds.
Article
Chemistry, Physical
Yuliang Liu, Haoyu Li, Eugene Yew Kun Tan, Erik Budi Santiko, Youhei Chitose, Manabu Abe, Shunsuke Chiba
Summary: In this study, we demonstrated the design and synthesis of PIqs with electron-withdrawing groups, which exhibit wider redox windows and higher triplet-state energies under visible light irradiation. By modifying the positions and structures of these electron-withdrawing groups, the photophysical and electrochemical properties of PIqs can be tailored, enabling a range of molecular transformations driven by visible light.
Article
Chemistry, Multidisciplinary
Yoshiya Sekiguchi, Jia Hao Pang, Jia Sheng Ng, Jiahua Chen, Kohei Watanabe, Ryo Takita, Shunsuke Chiba
Summary: Solvothermal treatment of 1-naphthylmethylamine with KH or n-BuLi / t-BuOK in THF results in two consecutive beta-hydride eliminations, yielding 1-naphthonitrile and KH. The freshly generated KH can undergo dearomative hydride addition to the resulting 1-naphthonitrile at the C4 position, forming alpha-cyano benzylic carbanion, which can be further functionalized to obtain 1,4-dihydronaphthalene-1-carbonitriles with a quaternary carbon center.
Article
Chemistry, Multidisciplinary
Haoyu Li, Yuliang Liu, Shunsuke Chiba
Summary: This perspective summarizes recent advances in using sulfur anions to promote molecular transformations under visible light irradiation, with focus on the role of sulfur anions in different reaction modes.
