Article
Chemistry, Organic
Xiya Cheng, Mengxuan Zhang, Guanyinsheng Qiu, Danqing Zheng
Summary: A reductive coupling reaction of sodium sulfinates has been developed for the synthesis of symmetrical/unsymmetrical thiosulfonates. The reaction proceeds under mild conditions in the presence of acetyl chloride and Hantzsch ester, showing broad functional group tolerance. Mechanistic studies suggest the involvement of a radical process.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Vera A. Vil', Valentina M. Merkulova, Alexey I. Ilovaisky, Stanislav A. Paveliev, Gennady Nikishin, Alexander O. Terent'ev
Summary: Fluorinated ketones were synthesized via electrochemical method in an undivided cell, with yields ranging from 20% to 85%.
Review
Chemistry, Organic
Wengui Wang, Shoufeng Wang
Summary: Minisci-type reactions involve the addition of carbon-centered radicals to basic heteroarenes followed by formal hydrogen atom loss. New radical generation strategies have expanded the variety of radical precursors that can be used, often operating under milder conditions. Radial generation methods based on photoredox catalysis and electrochemistry are popular approaches that are now available for synthetic chemists.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jin Choi, Gabriele Laudadio, Edouard Godineau, Phil S. Baran
Summary: This study presents a simple maleate-derived blocking group for the direct position-selective C-4 alkylation of pyridines, allowing for exquisite control and inexpensive access to valuable building blocks. The method is operationally simple and scalable, applied to access known structures rapidly and inexpensively, and signifies an interesting strategic departure in the use of Minisci chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Review
Chemistry, Multidisciplinary
P. David Bacos, Antti S. K. Lahdenpera, Robert J. J. Phipps
Summary: The Minisci reactions, characterized by the addition of carbon-based radicals to heteroarenes and subsequent rearomatization to form a carbon-carbon bond, have been widely used in medicinal chemistry. This article presents a catalytic strategy using bifunctional Bronsted acid catalysts to achieve regioselectivity and control the stereochemistry in Minisci reactions. The study also includes the development of a predictive model, mechanistic analysis, and synthetic improvements.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Yongliang Wei, Benjamin Ben-zvi, Tianning Diao
Summary: C-aryl glycosyl compounds offer improved in vivo stability compared to O- and N-glycoside analogues, making them attractive candidates for drug development and chemical biology studies. A new cross-coupling method has been developed for the preparation of C-aryl and heteroaryl glycosides, including nucleosides and 2-deoxysugars, from easily accessible glycosyl esters and bromoarenes, demonstrating the potential of this method in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Rupert S. J. Proctor, Padon Chuentragool, Avene C. Colgan, Robert J. Phipps
Summary: Minisci-type reactions are powerful methods for building complexity around basic heteroarenes. The disclosed method enables coupling of linear amides and heteroarenes with control of enantioselectivity at the newly formed stereocenter and site selectivity on both the heteroarene and the amide. This is achieved using a chiral phosphoric acid catalyst in conjunction with diacetyl as a combined hydrogen atom transfer reagent and oxidant, without the need for an extraneous photocatalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mohammed Sharique, Jadab Majhi, Roshan K. Dhungana, Lisa Marie Kammer, Matthias Krumb, Alexander Lipp, Eugenie Romero, Gary A. Molander
Summary: In this study, a simple, open-air, and efficient light-mediated Minisci C-H alkylation method is described, which is based on the formation of an electron donor-acceptor complex. Unlike previous protocols, this method does not require a photocatalyst, single electron transfer agent, or oxidant additive. The reaction can proceed under mildly acidic and open-air conditions, and it yields moderate to good amounts of Minisci alkylation products.
Article
Chemistry, Multidisciplinary
Avene C. Colgan, Rupert S. J. Proctor, David C. Gibson, Padon Chuentragool, Antti S. K. Lahdenpera, Kristaps Ermanis, Robert J. Phipps
Summary: This study reports a significant advancement in the catalytic enantioselective Minisci reaction, allowing the use of α-hydroxy radical coupling partners to obtain valuable enantioenriched secondary alcohol products. The approach is highly regioselective as well as highly enantioselective.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hao Zuo, Chen Zhang, Yang Zhang, Dawen Niu
Summary: A simple and general method for fully unprotected, stereoselective glycosylation of carboxylic acids was developed using bench-stable allyl glycosyl sulfones as donors. The reaction, conducted under basic conditions, showed high efficiencies and selectivities. Both the donor activation stage and the glycosidic bond forming stage were compatible with free hydroxyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zi-Tong Pan, Li-Miao Shen, Fentahun Wondu Dagnaw, Jian-Ji Zhong, Jing-Xin Jian, Qing-Xiao Tong
Summary: An efficient Minisci reaction of heteroarenes and unactivated C(sp(3))-H alkanes was achieved using inexpensive FeCl3 as a photocatalyst. The photogenerated chlorine radical participated in the hydrogen atom transfer of C-H, thereby initiating this reaction. Surprisingly, salt water and even seawater can serve as a chlorine radical source, offering an enlightening idea for future organic synthesis methods.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Chao Wang, Rupeng Qi, Zhaoqing Xu
Summary: This article summarizes the important application of radical-based reactions in glycosylation modifications, focusing on the synthesis of unnatural amino acids and the late-stage modification of peptides and proteins. It also provides an outlook on the future development in this direction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
M. R. Ajayakumar, Ji Ma, Andrea Lucotti, Karl Sebastian Schellhammer, Gianluca Serra, Evgenia Dmitrieva, Marco Rosenkranz, Hartmut Komber, Junzhi Liu, Frank Ortmann, Matteo Tommasini, Xinliang Feng
Summary: The synthesis of a previously unknown peri-heptacene (7-PA) with kinetically protected zigzag edges and high stability under inert conditions has been achieved. This compound displays open-shell and tetraradical characteristics, making it a potential modular approach for constructing next-generation n-peri-Acenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Barbara W. Hadrys, Robert J. Phipps
Summary: The study investigated the effect of solvent and Bronsted acid catalyst on regioselectivity in the addition of N -acetyl-substituted, alpha-amino alkyl radicals to quinolines. By adjusting the solvent and acid combination, conditions that strongly favor either C2 or C4 were identified, along with a limited scope of compatible substrates.
Article
Chemistry, Multidisciplinary
Yingwei Wang, Li-Fan Deng, Xia Zhang, Ze-Dong Mou, Dawen Niu
Summary: A general approach for making unnatural amino acids from cysteine derivatives was reported, utilizing an intramolecular radical substitution process to generate alkyl radicals. The generated alkyl radicals participated in diverse C-C bond forming events under mild, photocatalytic conditions at room temperature, and could be performed open to air. The utility of these transformations was further demonstrated in the straightforward synthesis of various previously inaccessible unnatural amino acids and peptides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Weidong Shang, Sheng-Nan Su, Rong Shi, Ze-Dong Mou, Guo-Qiang Yu, Xia Zhang, Dawen Niu
Summary: Glycosyl sulfoxides appended with an aryl iodide moiety are reported as stable precursors to glycosyl radicals, which can be converted rapidly and efficiently through intramolecular radical substitution for the synthesis of complex C-linked glycoconjugates under mild conditions, including glycopeptidomimetics and carbohydrate-DNA conjugates in aqueous media.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Li-Qiang Wan, Jin-Ge Cao, Dawen Niu, Xia Zhang
Summary: A general and mild approach for preparing alpha-branched aliphatic amines from imines is reported here. This method utilizes a cobalt-catalyzed umpolung alkylation of imines, employs easily available reaction partners, and demonstrates a broad substrate scope. Mechanistic studies suggest a radical pathway for this transformation.
Article
Chemistry, Multidisciplinary
Demeng Xie, Yingwei Wang, Xia Zhang, Zhengyan Fu, Dawen Niu
Summary: This research presents the use of alkyl sulfoxides as precursors to radicals in the synthesis of pyridine derivatives. It demonstrates that alkyl sulfoxides, N-methoxy pyridinium salts, and fluoride anions form electron donor-acceptor complexes in solution, which can undergo a radical chain process upon visible light irradiation to produce various pyridine derivatives efficiently. The broad scope of this reaction extends to different sulfoxides and N-methoxy pyridiniums. The synthetic versatility of sulfoxides as radical precursors adds to their significance as a useful tool in chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Han-Li Sun, Bin Wu, Da-Qi Liu, Zi-Di Yu, Jun-Jie Wang, Qianyi Liu, Xingchen Liu, Dawen Niu, Jin-Hu Dou, Rong Zhu
Summary: Here, we report the unexpected discovery of a Cu-catalyzed condensation polymerization reaction that converts simple C3 building blocks into polydiynes with C6 repeating units. This reaction utilized a simple system composed of a copper acetylide initiator and an electron-rich phosphine ligand to produce alkyne polymers with high yields, regioselectivity, and functional group compatibility. Hydrogenation of the resulting product yielded a new polyolefin-type backbone, while base-mediated isomerization led to a novel dienyne-based electron-deficient conjugated polymer. Mechanistic studies revealed an alpha-alpha selective Cu-catalyzed dimerization pathway of the C3 unit, followed by organocopper-mediated chain-growth propagation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Chen Zhang, Hao Zuo, Ga Young Lee, Yike Zou, Qiu-Di Dang, K. N. Houk, Dawen Niu
Summary: The chemistry of carbohydrates has a long history, and a simple, stereoselective and efficient glycosylation method is still needed for studying sugars. This study presents a strategy for 1,2-cis-glycosylation without using metals or strong acids. The method activates glycosyl donors through a radical cascade, resulting in the formation of 1,2-cis-glycosides with high stereoselectivity. The reaction shows remarkable tolerance to functional groups and is applicable to a broad range of donors.
Article
Multidisciplinary Sciences
Xiang Pu, Qiu-Di Dang, Lei Yang, Xia Zhang, Dawen Niu
Summary: The authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction that can selectively construct products with vicinal congested stereocenters. This reaction uses readily available starting materials, environmentally friendly catalysts, and has a broad substrate scope.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Qian Zhang, Wei Zhang, Ruoyan Cui, Yang Zhang, Dawen Niu
Summary: Here, we present the use of pyrimidinyl sulfones as electrophiles in Ni-catalyzed Suzuki-Miyaura cross-coupling reactions. This method enables the convenient synthesis of pharmaceutically relevant 2,4-disubstituted pyrimidines. The reactions proceed under mild conditions and exhibit a wide range of substrates. The efficient and regioselective cleavage of the C-sulfone bond is observed. Preliminary mechanistic studies suggest the crucial role of the alpha-nitrogen atom in pyrimidine in facilitating these transformations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Hongxin Zeng, Yanjing Li, Rongfeng Wu, Daqi Liu, Yang Zhang, Shiyang Xu, Dawen Niu
Summary: Here, a method for synthesizing carbohydrate-DNA conjugates by radical addition is reported. This method utilizes readily available, bench-stable, and unprotected glycosyl sulfinates as precursors to glycosyl radicals. The reaction, which is redox neutral, proceeds under mild and simple conditions and allows for a broad substrate scope. A small library of carbohydrate-DNA conjugates was successfully prepared.
Review
Chemistry, Multidisciplinary
Weidong Shang, Dawen Niu
Summary: The study of carbohydrates has become important in various fields due to their pivotal roles in cellular processes. Chemical glycosylation reactions are highly needed to explore their biological functions. Recent advances in radical pathway glycosylation have shown great potential in developing novel methods for glycoside synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Hao Zuo, Chen Zhang, Yang Zhang, Dawen Niu
Summary: A simple and general method for fully unprotected, stereoselective glycosylation of carboxylic acids was developed using bench-stable allyl glycosyl sulfones as donors. The reaction, conducted under basic conditions, showed high efficiencies and selectivities. Both the donor activation stage and the glycosidic bond forming stage were compatible with free hydroxyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Qingyi Zhao, Yandan Bao, Dawen Niu, Xuan Wang, Xiaojie Lu
Summary: In this study, we discovered two different S-glycosyl transformations in a DNA-encoded library (DEL)-compatible environment. One approach involves 2-chloro-1,3-dimethylimidazolidinium chloride (DMC)-mediated S-glycosylation, but it has limited substrate scope for DEL construction. We also investigated a photoinduced DNA-compatible S-glycosyl transformation using allyl sugar sulfones, which showed excellent compatibility with functional groups and yielded desired DNA-linked glycosyl derivatives. This pioneering DNA-compatible S-glycosyl transformation is a valuable tool for preparing glycosyl DELs and exploring sugar-incorporated delivery systems.
Article
Chemistry, Multidisciplinary
Liang Gong, Qian Zhang, Demeng Xie, Wei Zhang, Shi-Yang Xu, Xia Zhang, Dawen Niu
Summary: A Ni-catalyzed Negishi coupling reaction can prepare 1,2-dialkyl enol ethers in a stereoconvergent fashion, using alpha-oxy-vinylsulfones as electrophiles. This reaction shows unique selectivity and general applicability, indicating potential for further use in cross-coupling reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Hua Tang, Yu-Biao Tian, Hongyan Cui, Ren-Zhe Li, Xia Zhang, Dawen Niu
NATURE COMMUNICATIONS
(2020)
