Article
Chemistry, Multidisciplinary
Sudeshna Mondal, Chandan Kumar Giri, Mahiuddin Baidya
Summary: The weakly coordinating enaminone functionality is essential for the ruthenium-catalyzed C-H bond activation strategy, enabling the regioselective coupling of arenes with diazonaphthoquinones to produce polycyclic benzocoumarins in high yields. The protocol operates through a Ru(II)/Ru(IV) catalytic pathway and allows for the diversification of various pharmacophore-coupled substrates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yujia Gao, Juan Zhang, Wenyu Shan, Weihong Fei, Jinzhong Yao, Weijun Yao
Summary: In this study, a trimerization reaction of gamma-aryl-3-butynoates was achieved through catalysis, leading to the formation of exocyclopentene derivatives with an allcarbon quaternary stereocenter. The reaction exhibited high stereoselectivity and enantioselectivity, delivering optically pure products with high enantiomeric excess values.
Article
Chemistry, Multidisciplinary
Wanshu Wang, Song Zhou, Linjie Li, Yuanhang He, Xue Dong, Lu Gao, Qiantao Wang, Zhenlei Song
Summary: The unique small silacycle 3-silaazetidine can be easily prepared in situ from diverse air-stable precursors and shows excellent functional group tolerance in a palladium-catalyzed ring expansion reaction, giving diverse silaazacycle derivatives. These derivatives are promising ring frameworks for the discovery of Si-containing functional molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuan Zhong, Xiaoqiang Zhao, Xiaoyun Zhao, Dan Zhang, Wenli Li, Shouhui Wei, Fanhong Liu, Jihua Yu, Guichen Li, Dandan Wang
Summary: The green and atom-economical synthesis of functionalized 2-pyrrolines with two contiguous stereocenters was achieved using a catalytic amount of bifunctional chiral squaramide in a one-pot annulation reaction, providing good yields under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Yuhang Wang, Peng Ma, Ning Ma, Jianhui Wang
Summary: Ligand-controlled nickel-catalyzed selective cleavage of the C1-C2 or C1-C8 bond of benzocyclobutenones (BCBs) is reported. The delicate selection of dpppe or PMe3 as the ligand led to the predictable synthesis of a wide range of 1-naphthols and 2-naphthols without C2 and C3 substituents, respectively, from BCBs and potassium alkynyltrifluoroborate, and the increase in the amount of PMe3 resulted in tandem reaction of 2 equiv of BCB with the borate to afford 3,4,5-trisubstituted 2-naphthols. The fabulous ligand effect resulted in the facile and unique construction of multisubstituted naphthols with well-controlled regioselectivity and a high degree of structural diversity.
Article
Chemistry, Organic
Xue Li, Haohua Chen, Qingqing Xuan, Shaoyu Mai, Yu Lan, Qiuling Song
Summary: Inspired by the body circulation of Omeprazole, a novel carbenetriggered cascades for synthesizing 2-aminobenzofuran derivatives from N-sulfonyl-1,2,3-triazoles or benzothioazole-bearing thiocarbamates was disclosed, representing an unprecedented imine derivative migration process. Additionally, desulfurizing reagent-free Barton-Kellogg-type reactions starting from N-sulfonyl-1,2,3-triazoles were achieved for the first time, with elemental sulfur confirmed as a byproduct. Experimental data and DFT calculations further explained the unique reactivity observed in these reactions.
Article
Chemistry, Multidisciplinary
Xiaoming Jie, Chaohuang Chen, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The hydroboration of styrene or vinylcyclohexane with the IMes(C6F5)BH+ cation followed by deprotonation provides a convenient synthetic route to boraalkenes [B]=CHCH2R. The in-situ generated IMes(SCN)BH+ system reacts similarly with 1,1-diphenylethene, resulting in the formation of isothiocyanato-substituted boraalkene. The boraalkenes participate in [2+2] cycloaddition reactions with heterocumulenes, yielding respective four-membered heterocycles. The addition of borane HB(C6F5)(2) to [B]=CHCH2R+CO2 cycloadducts leads to cleavage of the central B-C sigma-bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hemanta Hazarika, Kangkana Chutia, Babulal Das, Pranjal Gogoi
Summary: An aryne-based synthetic protocol has been developed for the synthesis of 3-substituted-3-hydroxy-indolin-2-ones, yielding a wide variety of products in good yields. One of the synthesized compounds has been confirmed by single crystal XRD analysis. Treating the synthesized derivatives with an inorganic base at high temperature leads to an interesting o-arylated product of 1,3-cyclohexandione.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Andryj M. Borys, Eva Hevia
Summary: In this study, a new family of alkyne supported alkali-metal nickelates was reported. These compounds were synthesized through the combination of Ni(COD)(2), Ph-CuC-Ph, and the corresponding lithium aryl in a 2:1:4 ratio. They exhibited structural diversity and showed potential in catalyzing cyclotrimerization reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Wenxi Chen, Yan Mao, Min Wang, Fei Ling, Changchang Li, Zhangpei Chen, Jinzhong Yao
Summary: A rhodium-catalyzed formal [4 + 1]-cyclization reaction of aryl substituted pyrazoles with cyclopropanols via C-H bond activation/cyclization processes to selectively construct a series of carbonyl functionalized pyrazolo[5,1-a]isoindoles is reported. The reaction shows good functional group compatibility and a broad substrate scope with up to 84% yields. Mechanistic studies suggest that the C-H cleavage may be the rate-determining step in this transformation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Swagata Baruah, Sabera Sultana, Pratiksha Bhorali, Pallabi Saikia, Sanjib Gogoi
Summary: A novel Ru(ii)-catalyzed decarbonylative annulation and direct C-H functionalization reaction of phthalic anhydrides with acrylates is reported, providing an efficient route for the synthesis of 3,7-disubstituted phthalides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Changqing Ye, Yihang Jiao, Mong-Feng Chiou, Yajun Li, Hongli Bao
Summary: This study presents a metal-free method for the synthesis of pentasubstituted pyrroles and hexasubstituted pyrrolines with different substituents and a free amino group. The approach complements previous methods and supports the expansion of the toolbox for synthesizing valuable, but previously inaccessible, highly substituted pyrroles and pyrrolines. Mechanistic studies have been conducted to elucidate the reaction pathway.
Article
Chemistry, Organic
Yasunori Toda, Kayo Sato, Kensuke Sato, Kazuma Nagasaki, Hirotaka Nakajima, Ayaka Kikuchi, Kimiya Sukegawa, Hiroyuki Suga
Summary: This paper reports on the chiral binaphthyldiimine-Ni(II)-catalyzed asymmetric 1,3-dipolar cycloaddition reactions between acyclic carbonyl ylides generated from donor-acceptor oxiranes and aldehydes. Both aromatic and aliphatic aldehydes can be used as dipolarophiles, providing cis-1,3-dioxolanes with high diastereo- and enantioselectivities. Mechanistic studies suggest that a monomeric chiral Ni(II) complex acts as the active species for the cycloaddition, and the high levels of asymmetric induction can be explained by a concerted-asynchronous endo Si-face approach of the aldehyde.
Article
Chemistry, Organic
Ali Nikbakht, Kamran Amiri, Hormoz Khosravi, Yirong Zhou, Saeed Balalaie, Bernhard Breit
Summary: This novel copper-catalyzed cycloisomerization reaction provides a practical and efficient method for the synthesis of hexahydropyrrolo[3,4-b]azepin-5(4H)-ones by simultaneously forming four new bonds in a single step.
Article
Chemistry, Multidisciplinary
Xin-Lian Liu, Han-Ze Lin, Lu-Qi Tan, Jin-Bao Peng
Summary: In this article, an enantio-, site-, and E/Z-selective addition of ACPs with imines for the synthesis of dienyl substituted amines has been developed via palladium- and Bronsted acid co-catalysis. A range of synthetically valuable dienyl substituted amines were effectively prepared with good to excellent yields and excellent enantio- and E/Z-selectivities.
Article
Chemistry, Multidisciplinary
Huanan Wang, Hui Qian, Junliang Zhang, Shengming Ma
Summary: In this study, a palladium-catalyzed enantioselective carbon-phosphorus bond formation reaction affording axially chiral allenyl phosphonates has been developed. The reaction shows high enantioselectivity and good compatibility with a wide range of functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Juan Feng, Jiayi Shi, Lan Wei, Mingqing Liu, Zhiming Li, Yuanjing Xiao, Junliang Zhang
Summary: In this study, a highly regio- and diastereo-selective palladium/PC-Phos-catalyzed asymmetric Heck/Tsuji-Trost reaction was reported for the synthesis of various functionalized chiral hexahydroindoles with good yields and high enantioselectivity. The application of this reaction to the concise synthesis of (-)-alpha-Lycorane was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wenge Zhang, Pei-Chao Zhang, Yin-Lin Li, Hai-Hong Wu, Junliang Zhang
Summary: This study enables the synthesis of highly selective heterocycles through asymmetric cycloaddition reactions, providing an important method for efficient and selective reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Bin Yang, Kangning Cao, Guofeng Zhao, Junfeng Yang, Junliang Zhang
Summary: A Pd-catalyzed enantioselective three-component reaction has been developed for the synthesis of chiral gem-diarylmethine silanes. The reaction features a broad scope, high enantioselectivity, and mild conditions. It also allows easy access to enantiomers and has potential applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Jieming Zhang, Zhan-Ming Zhang, Qi Wu, Junliang Zhang
Summary: A Pd-catalyzed synthesis method for 1,2,3,4-tetrahydroisoquinoline (THIQ) was developed, involving oxidative addition, carbene insertion, and cyclization steps.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yin Yuan, Junfeng Yang, Junliang Zhang
Summary: In this study, a Cu-catalyzed enantioselective decarboxylative cyanation method via the merger of photocatalysis and electrochemistry was reported. This method provides an efficient and straightforward approach for decarboxylative coupling, eliminating the need for stoichiometric chemical oxidants or substrate prefunctionalization. Mechanistic insight on enantioselectivity control was obtained through DFT calculations.
Article
Chemistry, Multidisciplinary
Chun Ma, Yue Sun, Junfeng Yang, Hao Guo, Junliang Zhang
Summary: In this study, an efficient method for the catalytic synthesis of Troger's base analogues with nitrogen stereocenters was reported. The process involved palladium catalysis and the use of home-developed GF-Phos. The method allowed for the rapid construction of a new rigid cleft-like structure with both C and N stereogenic centers, exhibiting excellent efficiency and selectivity. Various applications as a chiral organocatalyst and metallic catalyst precursors were demonstrated, and DFT calculations revealed that NH center dot center dot center dot O hydrogen bonding and weak interaction between the substrate and ligand played crucial roles in achieving excellent enantioselectivity control.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Youshao Tu, Bing Xu, Qian Wang, Honglin Dong, Zhan-Ming Zhang, Junliang Zhang
Summary: In this work, we developed a highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction of o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This reaction features excellent regio-and enantiocontrol, high functional group tolerance, and easy scalability. More importantly, the demonstration of this method as a highly valuable tool for the construction of optically pure natural products (R)-tremetone and fomannoxin is highlighted.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Shiquan Gao, Chen Wang, Junfeng Yang, Junliang Zhang
Summary: In this study, an enantioselective intramolecular reductive coupling of enynes was achieved via the combination of electrochemistry and cobalt catalysis. The transition-metal catalyzed asymmetric cyclization of 1,6-enynes has been widely used for the construction of carbocycles and heterocycles, but examples under electrochemical conditions are rare. We report a Co-catalyzed enantioselective intramolecular reductive coupling of enynes using H2O as the hydride source, which provides good yields with high regio- and enantioselectivities. This study represents a rare progress on the cobalt-catalyzed enantioselective transformation via electrochemistry with a general substrate scope, and DFT studies suggest the possible reaction pathways.
NATURE COMMUNICATIONS
(2023)
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
Multidisciplinary Sciences
Jie Han, Siyuan Liu, Huanan Wang, Jie Wang, Hui Qian, Zhiming Li, Shengming Ma, Junliang Zhang
Summary: The 13-H elimination is a crucial step in the carbon-palladium bond quenching for the Heck reaction and has been a challenge to control enantioselectivity. Here, we developed a concise and efficient method to construct chiral allenes from fully substituted enol triflates through enantioselective 13-H elimination of alkenyl palladium species under mild conditions. The identified Xu-Phos catalysts play a crucial role in chemoselectivity and enantioselectivity. Multiple linear regression analysis shows the significance of steric effect on enantioselectivity. DFT calculations propose an intramolecular base-assisted deprotonation mechanism for this progress, and energy decomposition analysis suggests that the difference in electrostatic energy of the transition states dominates the stereoselectivity.
Review
Chemistry, Multidisciplinary
Bing Xu, Quanpu Wang, Chao Fang, Zhan-Ming Zhang, Junliang Zhang
Summary: This review summarizes the latest advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years. The review is organized into thirteen sections based on the different types of transformations involved. Chiral palladium catalysts have shown outstanding features in promoting a plethora of enantioselective cyclization reactions, providing convenient access to structurally diverse chiral carbo- and hetero-cycles.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Zhi-Mao Zhang, Junliang Zhang, Quan Cai
Summary: In this study, seven pentacyclic 19-nor-clerodane diterpenoids were collectively synthesized using an asymmetric reaction. A key feature of the synthesis was the generation of a versatile intermediate through late-stage oxidation state adjustments. This study provides a concise and efficient synthetic route for these compounds.
Article
Chemistry, Multidisciplinary
Huanan Wang, Hui Qian, Junliang Zhang, Shengming Ma
Summary: A new reaction method for the synthesis of axially chiral allenyl phosphonates through palladium-catalyzed carbon-phosphorus bond formation has been developed. The reaction exhibits high yields and enantioselectivity, and can accommodate a wide range of functional groups. Mechanistic studies have revealed an important kinetic resolution process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yue Sun, Chun Ma, Zhiming Li, Junliang Zhang
Summary: This article reports an efficient method for the synthesis of chiral pyrrolidines and piperidines through a palladium-catalyzed carbenylative amination reaction of N-tosylhydrazones and (E)-vinyl iodides. The reaction shows high selectivity and good yields, and can be easily scaled up. It also enables the efficient synthesis of a natural product (-)-norruspoline.
