Article
Chemistry, Multidisciplinary
Aitor Bermejo-Lopez, Wei-Jun Kong, Pedro J. Tortajada, Daniels Posevins, Belen Martin-Matute, Jan-E Backvall
Summary: A novel iron-catalyzed borylation reaction of propargylic acetates leading to allenylboronates has been developed. This method allows the preparation of di-, tri-, and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-S(N)2' displacement of acetate by boron occurs, allowing chirality transfer to yield enantiomerically enriched allenylboronates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Nabakumar Bera, Bhabani Sankar Lenka, Sangita Bishi, Shantanu Samanta, Debayan Sarkar
Summary: A new mechanistic pathway of propargylic alcohol activation by gold(I) catalysis has been proposed, which efficiently synthesizes pyrroles, pyridinones, and indoles. Control experiments confirm the formation of an allene oxide intermediate through the participation of the oxygen atom of propargylic alcohol, and this method is successfully applied to the synthesis of hydroxyalkyl indoles and benzofurans.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shuting Zhang, Shuaijie Wu, Qiang Wang, Shiji Xu, Ying Han, Chao-Guo Yan, Junliang Zhang, Lei Wang
Summary: This article reports the first palladium-catalyzed asymmetric alleneamination of beta,gamma-unsaturated hydrazones with propargylic acetates. The reaction enables the efficient installation of various multisubstituted allene groups onto dihydropyrazoles in good yields with excellent enantioselectivities. The salient features of this reaction include readily available starting materials, a broad substrate scope, easy scale-up, mild reaction conditions, and versatile transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Shengrong Liao, Huayan Xu, Liang Xu, Baoxia Liang, Bin Yang, Junfeng Wang, Xuefeng Zhou, Xiuping Lin, Zaigang Luo, Yonghong Liu
Summary: In this study, a gold-catalyzed hydroarylation reaction was used to synthesize various terminal aryl-substituted allylic alcohols with moderate to high yields under mild conditions.
Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In recent years, significant progress has been made in the development of transition metal-catalyzed enantioselective propargylic substitution reactions. However, until now, no successful example with phosphorus-centered nucleophiles has been reported. This study presents the first successful example of ruthenium-catalyzed enantioselective propargylic substitution reactions using propargylic alcohols as substrates and diarylphosphine oxides as phosphorus-centered nucleophiles, providing a new method for preparing chiral phosphorus-containing organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dong Li, Wande Zhang, Shuaibo Zhang, Wuding Sun, Jinfeng Zhao, Baomin Wang, Jingping Qu, Yuhan Zhou
Summary: This study describes the first asymmetric trifluoromethylated allylic alkylation of pyrazolones using a novel trifluoromethylated allylation reagent. The reaction affords functionalized chiral pyrazolones with high yields and excellent selectivities. The double-bond migration of alpha-(trifluoromethyl)alkenyl acetates is identified as an initial and interesting step in the mechanism. Additionally, this study is significant in providing a novel and widely applicable trifluoromethyl-containing allylation reagent.
Article
Chemistry, Organic
Guo-Ke Zhang, Shu-Fang Wu, Chen Zhong, Yu-Qi Liu, Da-Hua Wang, Yu-Chen Zhang, Feng Shi
Summary: A copper-catalyzed alpha,beta-regioselective (2+4) cycloaddition of propargylic esters with o-hydroxyphenyl substituted secondary phosphine oxides (SPOs) was established, which afforded phosphorus-containing six-membered heterocycles in high yields. This reaction not only represents the first alpha,beta-regioselective (2+n) cycloaddition of propargylic esters via the intermediates of copper-allenylidenes, but also represents the first application of o-hydroxyphenyl substituted SPOs as 1,4-dinucleophiles in (2+4) cycloadditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Taibei Fang, Shiwen Zhang, Qingqing Ye, Shuwen Kong, Tingting Yang, Kaijie Tang, Xinwei He, Yongjia Shang
Summary: A sequential Rh(III)-catalyzed C-H activation/annulation of N-hydroxybenzamides with propargylic acetates has been developed to form NH-free isoquinolones. This reaction involves a sequential C-H activation/alkyne insertion/intramolecular annulation/N-O bond cleavage procedure, producing a broad range of products with diverse substituents in moderate-to-excellent yields. Notably, this protocol allows for the simultaneous formation of two new C-C/C-N bonds and one heterocycle in one pot, with water as the sole byproduct.
Article
Chemistry, Physical
Jin-Tao Xia, Ling Li, Xiang-Ping Hu
Summary: A copper-catalyzed asymmetric decarboxylative propargylic alkylation has been successfully achieved, allowing for the highly stereoselective formation of acyclic vicinal tri- and tetrasubstituted stereocenters. This strategy has demonstrated high potential in resolving challenges present in traditional catalytic propargylic alkylation by preparing optically active quaternary alpha-amino acid esters with chiral tertiary propargylic moieties in high yields and good to excellent diastereo- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Antonio Arcadi, Giancarlo Fabrizi, Andrea Fochetti, Francesca Ghirga, Antonella Goggiamani, Antonia Iazzetti, Federico Marrone, Giulia Mazzoccanti, Andrea Serraiocco
Summary: The palladium-catalyzed benzylic-like nucleophilic substitution of benzofuran-2-ylmethyl acetate with N, S, O and C soft nucleophiles was investigated, showing different catalytic systems have significant effects on the reaction outcome, with nucleophilic substitution only occurring at the benzylic position.
Article
Chemistry, Multidisciplinary
Zhiheng Li, Danran Li, Huaming Xiang, Jian Huang, Yinuo Zheng, Cuiju Zhu, Xiuling Cui, Chao Pi, Hao Xu
Summary: In this study, a highly enantioselective propargylic substitution reaction of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand was disclosed. This strategy shows broad substrate compatibility, mild reaction conditions, excellent yields with remarkable enantioselectivity, and enables the synthesis of diverse products.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Gilles De Smet, Xingfeng Bai, Carl Mensch, Sergey Sergeyev, Gwilherm Evano, Bert U. W. Maes
Summary: This study demonstrates that acetate can serve as a renewable leaving group for selective deoxygenation of phenolics. The Ni-catalyzed reaction in a green solvent allows for efficient deoxygenation without affecting specific functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zijun Huang, Jia Tang, Xiongwei Jiang, Tianle Xie, Minmin Zhang, Donghui Lan, Shaofeng Pi, Zhengde Tan, Bing Yi, Yuehui Li
Summary: In this study, a ligand-free iron catalyst is used for the hydroaminocarbonylation of alkynes using NH4HCO3 as the ammonia source, enabling the efficient and regioselective synthesis of linear α,β-unsaturated primary amides. The method provides a valuable approach for the synthesis of important intermediates and building blocks in organic synthesis.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Huan Yan, Gaochen Xu, Meng Gu, Sai Zhang, Qinghuan Wu, Jingjing Meng, Ning Zhu, Zheng Fang, Jindian Duan, Kai Guo
Summary: A novel synthesis method for trifluoromethyl-containing 2H-1,3-oxazines was developed by catalytically oxidizing alpha,beta-unsaturated ketoxime acetates with ethyl trifluoropyruvate. This procedure provides an alternative route towards functionalized 2H-1,3-oxazines.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yu-Jiang Wang, Yuan Zhang, Zou Qiang, Jia-Ying Liang, Zili Chen
Summary: A gold-catalyzed formal intermolecular [2+3] cyclo-coupling between 1,3-enynes and phenols was developed to synthesize dihydrobenzofuran derivatives with the addition of 2,6-dichloropyridine N-oxide. This method achieved highly ortho-selective phenol SEAr functionalization using 1,3-enynes as alpha-oxo vinyl gold carbenoid surrogates.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Zhitong Zheng, Youliang Wang, Xu Ma, Yuxue Li, Liming Zhang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Ting Li, Yuhan Yang, Baomin Luo, Bo Li, Luyi Zong, Weiguang Kong, Hao Yang, Xinpeng Cheng, Liming Zhang
Article
Chemistry, Organic
Ke Zhao, Yu-Chen Hsu, Ziguang Yang, Rai-Shung Liu, Liming Zhang
Review
Chemistry, Multidisciplinary
Zhitong Zheng, Xu Ma, Xinpeng Cheng, Ke Zhao, Kaylaa Gutman, Tianyou Li, Liming Zhang
Summary: Homogeneous gold catalysis has seen significant development since the turn of the millennium, with oxidative gold catalysis being a vibrant subfield delivering valuable synthetic methods. This comprehensive review covers the mechanistic aspects, oxidants, and synthetic applications of oxidative gold catalysis.
Article
Chemistry, Physical
Ting Li, Xinpeng Cheng, Pengcheng Qian, Liming Zhang
Summary: Through cooperative gold catalysis enabled by a special ligand, intramolecular asymmetric functionalization of unactivated propargylic C-H bonds has been achieved, yielding chiral cyclopentane/cyclohexane-fused homopropargylic alcohols with excellent enantiomeric excesses. The reaction shows a broad scope, high stereoselectivity and is realized under mild reaction conditions. Density functional theory studies support the reaction mechanism and confirm metal-ligand cooperation.
Article
Chemistry, Multidisciplinary
Xu Ma, Zhitong Zheng, Yue Fu, Xijun Zhu, Peng Liu, Liming Zhang
Summary: This study introduces a strategy for the formation of 1,2-cis-glycosidic linkage using gold catalysis, achieving excellent yields and outstanding selectivities under mild conditions. This strategy is also successfully applied to the synthesis of oligosaccharides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xinpeng Cheng, Tianyou Li, Kaylaa Gutman, Liming Zhang
Summary: This study successfully synthesized alpha,beta-Butenolides with high enantiomeric excess using a novel Cu(I)-ligand cooperative catalysis, highlighting the importance of cooperation between the metal center and the ligand basic amino group. Moreover, it was found that other coinage metals such as Ag and Au can also play a similar role in this asymmetric isomerization chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xinpeng Cheng, Liming Zhang
Summary: This work describes an asymmetric gold-ligand cooperative catalysis for the transformation of readily accessible chiral/achiral propargylic sulfonamides into chiral 3-pyrrolines. A bifunctional biphenyl-2-ylphosphine ligand containing a chiral tetrahy-droisoquinoline fragment is crucial for the observed metal-ligand cooperation and asymmetric induction. The reaction can provide 2,5-cis-3-pyrrolines with excellent diastereoselectivities in a matched scenario, and 2,5-trans-3-pyrrolines with >5/1 diastereoselectivity in a mismatched scenario using the ligand enantiomer. The synthetic utilities of this chemistry have been demonstrated.
Article
Chemistry, Multidisciplinary
Ke Zhao, Philip Kohnke, Ziguang Yang, Xinpeng Cheng, Shu-Li You, Liming Zhang
Summary: A gold(I)-catalyzed enantioselective dearomatization is achieved through metal-chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl-2-ylphosphines is developed for rapid access to these ligands, enabling broad substrate scope. The selective acceleration of one enantiomer formation is achieved through hydrogen bonding between substrate and ligand remote basic group, leading to enantiomeric excesses up to 98%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xu Ma, Yongliang Zhang, Xijun Zhu, Yongliang Wei, Liming Zhang
Summary: This work introduces a novel catalytic S(N)2 glycosylation method using an amide-functionalized 1-naphthoate platform as a latent glycosyl leaving group. The amide group facilitates the S(N)2 process by directing the attack of the glycosyl acceptor via H-bonding interaction, resulting in stereoinversion at the anomeric center. Additionally, the amide group enables a safeguarding mechanism by trapping oxocarbenium intermediates, minimizing stereorandom S(N)1 processes. This strategy allows for high-yielding synthesis of a wide range of glycosides with stereoinversion, including challenging 1,2-cis-linkage-rich oligosaccharides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Philip Kohnke, Liming Zhang
Summary: Expedient access to bridged enol benzoates is achieved through a tandem gold-catalyzed cycloisomerization of enynyl esters and the Diels-Alder reaction. The gold catalysis enables the use of enynyl substrates without additional propargylic substitution and results in highly regioselective formation of less stable cyclopentadienyl esters. The regioselectivity is facilitated by a bifunctional phosphine ligand with a remote aniline group that promotes alpha-deprotonation of a gold carbene intermediate. The reaction is applicable to different alkene substitution patterns and various dienophiles.
Article
Chemistry, Multidisciplinary
Yongliang Zhang, Ke Zhao, Xinyi Li, Carlos D. Quintanilla, Liming Zhang
Summary: By using a chiral bifunctional phosphine ligand, a highly efficient and enantioselective dearomatization of phenols is achieved through metal-ligand cooperation. The reaction shows great generality by allowing substitutions at various positions of benzene, including electron-withdrawing groups and carbon-based groups. Spirocyclohexadienone-pyrrol-2-ones, spirocyclohexadienone-butenolides, and spirocyclohexadenone-cyclopentenones are formed in high yields and with high enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Carlos D. D. Quintanilla, Ke Zhao, Liming Zhang
Summary: By combining tandem asymmetric gold catalysis and subsequent stereoconvergent hydrolysis, hydroxylated propargylic esters are transformed into chiral β-oxygenated ketones with good enantiomeric ratios and high yields. The chiral center of the product is formed through stereoselective cyclization of a hydroxylated allenyl ester intermediate facilitated by asymmetric gold-ligand cooperation.
Review
Chemistry, Multidisciplinary
Zhao Ke, Hong Zhi, Zhang Liming
Summary: Homogeneous asymmetric gold catalysis has experienced significant development since 2005 and has been extensively applied in organic synthesis. In recent years, the development of chiral functionalized biaryl-2-ylphosphine ligands has opened up new approaches for achieving asymmetric gold catalysis, focusing on the enabling interactions between ligand functional groups and substrates.
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE
(2021)
Article
Chemistry, Multidisciplinary
Xiaojun Hu, Bingwei Zhou, Hongwei Jin, Yunkui Liu, Liming Zhang
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
