Article
Chemistry, Applied
Brigita Mudrakova, Peter Kisszekelyi, Denisa Vargova, Dorota Zakiewicz, Radovan Sebesta
Summary: This paper presents a highly enantio- and diastereoselective tandem transformation method, using Cu-catalyzed conjugate addition of Grignard reagents to heterocyclic Michael acceptors, followed by one-pot trapping of in situ formed enolates with stabilized carbocations or their equivalents. This method allows the installation of structurally attractive substituents on heterocyclic compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Wenjun Luo, Li-Ming Zhang, Zhan-Ming Zhang, Junliang Zhang
Summary: A novel family of PNP ligands (W-Phos) was designed and applied in the copper-catalyzed asymmetric addition of linear Grignard reagents to aryl alkyl ketones. This method allows for the facile synthesis of versatile chiral tertiary alcohols with high yields and excellent enantioselectivities. It also has the potential for the synthesis and modification of various densely functionalized medicinally relevant molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gleb A. Chesnokov, Karl Gademann
Summary: The marine-derived compound Peyssonnoside A was successfully synthesized for the first time in a concise, efficient, scalable, and highly diastereoselective manner. The aglucone peyssonnosol was achieved in 21% overall yield after 15 steps, with key reactions including Simmons-Smith cyclopropanation and Mukaiyama hydration controlled by the spatial structure of the substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Kang-Ji Gan, Fu-Qiang Ni, Zhihan Zhang, Yao Zhu
Summary: The concise total synthesis of salimabromide was achieved using a series of novel reactions, which allowed for the construction of its unique carbon skeleton and stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Li-Ming Zhang, Wenjun Luo, Jiangzhen Fu, Yu Liu, Junliang Zhang
Summary: A newly developed PNP-type W-Phos ligand showed a unique effect on the catalytic asymmetric addition of reactive Grignard reagents to ketimines. This enabled a Cu(I)-catalyzed asymmetric alkylation reaction of N-sulfonyl ketimines, resulting in the formation of optically active α-tertiary amines with high enantioselectivities.
Article
Chemistry, Multidisciplinary
Hyotaik Kang, Chao-Jun Li
Summary: This study presents the use of umpolung aldehydes as carbanion equivalents for highly regioselective 1,6-conjugate addition reactions to unsaturated ketones, with initial investigation into the enantioselective variant. It was found that the synergy of ruthenium(ii) catalyst and electron-rich, bidentate phosphine ligand is crucial for enhancing reactivity and selectivity under mild reaction conditions.
Article
Chemistry, Organic
Maximilian Kaiser, David Schoenbauer, Katharina Schragl, Matthias Weil, Peter Gaertner, Valentin S. Enev
Summary: This paper describes our efforts towards the total synthesis of natural product elisabethin A. The first approach focuses on the proposed biosynthesis, assembling the 6,6-ring system before forming the five-membered ring including the quaternary carbon. The second approach involves a high yielding cyclization under Mitsunobu conditions as a key step, leading to the preparation of an unusual and highly functionalized bicyclic 6,5-spiro compound. Both routes share a common advanced precursor obtained from an underdeveloped Claisen rearrangement of an aryl dienyl ether.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jiahua Chen, Jun Wei Lim, Derek Yiren Ong, Shunsuke Chiba
Summary: The synthesis of alpha-tertiary amines was achieved by iteratively adding carbon nucleophiles to N,N-dialkyl carboxamides, forming anionic tetrahedral carbinolamine intermediates. These intermediates were then treated with bromotrimethylsilane followed by organomagnesium or organolithium reagents to produce alpha-tertiary amines. The use of (trimethylsilyl)methylmagnesium bromide as the second nucleophile allowed for aza-Peterson olefination, resulting in the formation of 1,1-diarylethylenes after acidic work-up.
Article
Chemistry, Multidisciplinary
Won Jun Jang, Jeongkyu Woo, Jaesook Yun
Summary: The study reported a method to synthesize enantioenriched alkylboron compounds through conjugate addition, which are influenced by two contiguous carbon stereogenic centers, with high yield and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Junwen Wang, Jun Li, Yan Wang, Sisi He, Hengzhi You, Fen -Er Chen
Summary: In this study, a polymer-supported chiral heterogeneous copper catalyst was reported, which demonstrated high reactivity and enantioselectivity in asymmetric conjugate addition reactions.
Article
Chemistry, Multidisciplinary
Daniels Posevins, Aitor Bermejo-Lopez, Jan-E. Backvall
Summary: An iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents was disclosed, allowing for efficient chirality transfer and preparation of various fluoroalkyl allenes. Additionally, an iron-catalyzed cross-coupling of Grignard reagents with alpha-alkynyl oxetanes and tetrahydrofurans was demonstrated as a straightforward approach towards fully substituted beta- or gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu-Chao Wang, Zhao-Xin Xiao, Miao Wang, Shao-Qian Yang, Jin-Biao Liu, Zhi-Tao He
Summary: This study presents modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis, which has been considered unfeasible. The results show that the 1,5-conjugate addition products can be conveniently transformed into various privileged enantioenriched motifs, indicating the potential applications of this method in synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Rina Takahashi, Anqi Hu, Pan Gao, Yunpeng Gao, Yadong Pang, Tamae Seo, Julong Jiang, Satoshi Maeda, Hikaru Takaya, Koji Kubota, Hajime Ito
Summary: This study presents a method for the general mechanochemical synthesis of magnesium-based carbon nucleophiles in air using a ball milling technique, which avoids the drawbacks of using dry organic solvents and long reaction times.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yong-Wang Huo, Xinxin Qi, Xiao-Feng Wu
Summary: This study developed a new method for synthesizing alpha,beta-unsaturated thioesters via nickel-catalyzed thiocarbonylation reaction of vinyl triflates with arylsulfonyl chlorides. By using Mo(CO)(6) as both CO source and reductant, alpha,beta-unsaturated thioesters were obtained in moderate to good yields with excellent functional group compatibility. It is notable that this is the first example of nickel-catalyzed carbonylative synthesis of alpha,beta-unsaturated thioesters using arylsulfonyl chlorides as the coupling partner.
Article
Chemistry, Multidisciplinary
Jinbin Zhu, Zhenyue Li, Jiaqi Li, Duanshuai Tian, Ronghua Xu, Zhiyong Tan, Zhengwang Chen, Wenjun Tang
Summary: In this report, an efficient rhodium-catalyzed addition of arylboronic acids to N-heteroaryl ketones is established, affording a variety of valuable alpha-heteroaryl alcohols with excellent functional group compatibility. The employment of the WingPhos ligand containing two anthryl groups is crucial for this transformation.
Article
Chemistry, Organic
Xin-Yu Liu, Yan-Wei Zhao, Tian Jiang, Weidong Rao, Shun-Yi Wang
Summary: A new method for the synthesis of benzothiazole derivatives through the reaction of 2-halo-N-allylanilines with K2S in DMF has been developed. This reaction is initiated by the trisulfur radical anion S-3(center dot-), generated in situ from K2(S) in DMF, without the need for transition-metal catalysis or other additives. In addition to forming two C-S bonds, the heteroaromatization of benzothiazole is triggered by radical cyclization and H-shift.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Cheng-Mi Huang, Jian Li, Shan-Le Wang, Jing-Jing Ai, Xin-Yu Liu, Wei-Dong Rao, Shun-Yi Wang
Summary: An efficient transition-metal-free decarboxylative cyclization of N-arylacrylamides with 2,2-difluoro-2-(phenylthio)acetic acid for the construction of thiodifluoroindoleone derivatives has been described. The strategy features stable and readily available substrates, mild reaction conditions, and transition-metal-free catalysts. This protocol has also been successfully applied to the synthesis of gem-difluoroalkenes found in numerous biologically active compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ying Chen, Fei Wang, Bo-Xi Liu, Wei-Dong Rao, Shun-Yi Wang
Summary: A Ni(ii)-catalyzed reductive cross-coupling reaction has been developed for the synthesis of benzylic sulfides/selenides from oxalates and thiosulfonates/selenosulfonates under mild conditions. The use of oxalates prepared from corresponding alcohols as carbon radical precursors in the reaction provides an easy substrate availability and mild reaction conditions, offering a new method for the preparation of unsymmetrical sulfides/selenides with good functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Fei Wang, Ying Chen, Weidong Rao, Lutz Ackermann, Shun-Yi Wang
Summary: In this work, the authors present a new method for the synthesis of disulfides through a reductive nickel-catalyzed cross-electrophile coupling of unactivated alkyl bromides with symmetrical tetrasulfides, forming unsymmetrical disulfide intermediates. This approach offers practicality and scalability for disulfide synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shi-Yin Tian, Jing-Jing Ai, Jia-Hui Han, Weidong Rao, Shu-Su Shen, Daopeng Sheng, Shun-Yi Wang
Summary: A photocatalytic synthesis method was developed to simultaneously construct two C-S/Se bonds and one C-C bond without the use of transition metals or other additives, using diphenyl disulfide or diphenyl diselenide as sulfur or selenium sources.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zhenguo Zhang, Jun Gu, Yongheng Lv, Liang Ji, Xiaoxiao Liu, Beishen Wu, Fang Liu, Zhenhua Jia, Teck-Peng Loh
Summary: A metal-free synthesis of β-carbolines from tryptamines and aromatic aldehydes is achieved using a triaryl carbenium ion pair as a catalyst. This method exhibits excellent functional group tolerance and is demonstrated with the synthesis of Eudistomin U and fluorescent compounds on a large scale. Mechanistic studies reveal the formation of a trityl radical through a single-electron transfer process and its trapping by an oxygen molecule. In addition, an in-situ-generated reactive oxygen-centered radical is found to be essential for the efficient dehydroaromatization process.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Organic
Ying Chen, Fei Wang, Weidong Rao, Shusu Shen, Daopeng Sheng, Shun-Yi Wang
Summary: An efficient method for the copper-catalyzed ring-opening hydrolysis of silacyclobutanes to silanols was developed in this study. This strategy offers the advantages of friendly reaction conditions, simple operation, and good functional group compatibility. It also allows for the introduction of S-S bonds into organosilanol compounds in a single step. The successful gram scale synthesis demonstrates the potential of this protocol for practical industrial applications.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Letter
Chemistry, Organic
Yi-Fan Jiang, Wei-Chen Zhu, Xin-Yu Liu, Shi-Yin Tian, Jia-Hui Han, Weidong Rao, Shu-Su Shen, Daopeng Sheng, Shun-Yi Wang
Summary: Here, a new method is provided to synthesize 1,3-dibenzenesulfonylpolysulfane (DBSPS), which reacts with boronic acids to produce thiosulfonates. Commercially available boron compounds significantly expand the range of thiosulfonates. Experimental and theoretical investigations reveal that DBSPS can generate both thiosulfone and dithiosulfone fragments, with the latter being unstable and decomposing into thiosulfonates.
Article
Chemistry, Organic
Wang Chen, Xin-yu Liu, Daopeng Sheng, Yi-Fan Jiang, Weidong Rao, Shu-Su Shen, Zhao-Ying Yang, Shun-Yi Wang
Summary: A nickel-catalyzed C-SS reductive cross-coupling reaction for producing unsymmetric disulfides has been developed. This approach exhibits a broad substrate scope, excellent functional group tolerance, and can be conducted under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jia-Hui Han, Shi-Yin Tian, Weidong Rao, Shu-Su Shen, Daopeng Sheng, Shun-Yi Wang
Summary: In this study, a visible-light-mediated selenylation/cyclization reaction using selenium radicals generated from diselenides as radical sources with acrylimide derivatives is described. This method provides a mild and effective approach for the synthesis of symmetrical selenosubstituted pyrrolidine-2,5-diones. The described catalytic strategy offers advantages such as mild reaction conditions, metal-free conditions, no additives required, easy operation, and a wide substrate range.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Fei Wang, Ying Chen, Weidong Rao, Shu-Su Shen, Shun-Yi Wang
Summary: A Cu-catalyzed cascade reaction has been developed for the construction of S (Se)-containing organosilicon compounds using four-membered silacyclobutanes (SCBs) and thiosulfonates. The protocol exhibits a wide substrate scope, high functional group compatibility, and mild reaction conditions, enabling the formation of new C-S (Se) and Si-O bonds in a single step.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ying Chen, Daopeng Sheng, Fei Wang, Weidong Rao, Shu-Su Shen, Shun-Yi Wang
Summary: A Ni(II)/TPMPP-catalyzed reductive cross-coupling reaction has been reported for the synthesis of unsymmetric disulfides from benzyl oxalates and tetrasulfides. This method offers mild reaction conditions, wide substrate range, and easy operation, and has successfully achieved gram-scale synthesis of disulfides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Fei Wang, Ying Chen, Lutz Ackermann, Shun-Yi Wang
Summary: In this study, a selective cross-coupling reaction between unactivated alkyl bromides and diaryl tellurides was achieved using reductive nickel catalysis, leading to the synthesis of unsymmetrical alkyl-aryl tellurides with mild reaction conditions, high yields, easily accessible substrates, and a broad substrate scope.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Bo-Xi Liu, Fei Wang, Ying Chen, Wei-Dong Rao, Shu-Su Shen, Shun-Yi Wang
Summary: A visible-light-promoted regioselective denitrogenative cross-coupling between benzotriazinones and selenosulfonates has been developed for the synthesis of ortho-selenylated benzamides. The reaction provides good yields and demonstrates a general substrate scope. Furthermore, this protocol has been successfully employed for the one-pot two-step synthesis of a series of ebselen and its analogs.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Lin Xu, Pei Xu, Yi-Ming Zhu, Weidong Rao, Shun-Yi Wang
Summary: This new method utilizes NaI/TBHP as catalyst to synthesize achiral axial 3,3'-biindole-2,2'-dibenzenesulfonothioate derivatives from arylsulfonyl hydrazides and indole-2-thiones under mild conditions without the need for a transition-metal catalyst.
ORGANIC CHEMISTRY FRONTIERS
(2021)