Article
Chemistry, Physical
Ramon Arora, Regina M. Oechsner, Clara Jans, Bijan Mirabi, Austin D. Marchese, Mark Lautens
Summary: A palladium-catalyzed epimerization reaction of stereogenic alkyl iodides is reported using an air-stable precatalyst. Mechanistic experiments revealed the stereoinversion of the C-I bond via reversible bond formation, supported by density functional theory studies. Stoichiometric experiments showed that irradiation of isolable alkyl-Pd(II) complexes promoted C-I reductive elimination, with potential application in C-Br bond formation.
Article
Chemistry, Multidisciplinary
Qianyi Ge, Jingjie Meng, Huikang Liu, Zehua Yang, Zhengxing Wu, Wanbin Zhang
Summary: In this study, a Pd-catalyzed long-range olefin isomerization (up to 15 units) for general aryl olefins via a 1,2-hydrogen shift mechanism is reported. This method provides a simple pathway to long-range olefin isomerization without the participation of special ligands or co-catalysts.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Peng Wang, Ji Yang, Kangkang Sun, Helfried Neumann, Matthias Beller
Summary: The direct palladium-catalyzed selective carbonylative coupling of less reactive aryl chlorides with primary and secondary amines is achieved using a palladium/Xantphos catalyst system and cesium chloride as an additive. This reaction shows high conversion for various aryl chlorides and good functional group compatibility.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Adesh Kumar Singh, Rapelly Venkatesh, Vimlesh Kumar Kanaujiya, Varsha Tiwari, Jeyakumar Kandasamy
Summary: An efficient method for the synthesis of C-1 aryl enones from aryl iodides and glycal enones through palladium-catalyzed cross-coupling reactions under ligand-free conditions was developed. This method is applicable to a wide range of aryl iodides with different electron-donating and withdrawing groups, and can be carried out under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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
Shengzu Duan, Guogang Deng, Yujin Zi, Xiaomei Wu, Xun Tian, Zhengfen Liu, Minyan Li, Hongbin Zhang, Xiaodong Yang, Patrick J. Walsh
Summary: This study introduces a unique enantioselective nickel-catalyzed vinylation method for the synthesis of diverse vinyl aryl methyl amines and enantioenriched 1,3-diamine derivatives, which are frequently found in natural products and medications. The success of this method relies on a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, enabling an anionic vinylation route over a background radical reaction. Scalability and synthetic potential of this method are confirmed through a telescoped gram scale synthesis and product derivatization study.
Article
Chemistry, Multidisciplinary
Chen Chen, Liying Liu, Wan Sun, Bolin Zhu
Summary: By utilizing a palladium-catalyzed cascade strategy, an intermolecular aryl-carbamoylation of unactivated alkenes was developed under mild conditions, providing access to diverse aryl-functionalized oxindoles in moderate to good yields.
Article
Chemistry, Organic
Fucheng Yin, Yifan Chen, Zhongwen Luo, Shang Li, Lingyi Kong, Xiaobing Wang
Summary: This study demonstrates the application of aryl halides in organic synthesis, specifically focusing on the usage of methyl 2-bromobenzoate and 2-nitrophenyl iodides as mild and effective bromination and iodination reagents. This efficient cascade catalysis method can be applied to the total synthesis of natural products Mafaicheenamine A and Claulamine A.
Article
Chemistry, Organic
Xia-Bin Xiang, Sheng Wang, Teng Xu, Shanshan Chen
Summary: An effective Pd-catalyzed regioselective hydroesterification of 1,3-conjugated enynes with aryl formates was found, achieving selective formation of 2-ester-substituted 1,3-dienes in good yields with excellent regioselectivities using the Pd-CyDPEphos catalytic system.
Article
Chemistry, Organic
Xin Fu, Tingting Ran, Yu Zhou, Jie Liu
Summary: Here, a facile and efficient electrochemical promoted Ni-catalyzed reductive carbon-carbon bond formation is reported. This Nicatalyzed modular approach shows good functional group tolerance and broad substrate scope. It enables the synthesis of a series of allylic compounds, including various structurally complex natural products and pharmaceutical motifs.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wenjun Miao, Chuanfa Ni, Pan Xiao, Rulong Jia, Wei Zhang, Jinbo Hu
Summary: This novel nickel-catalyzed reductive cross-coupling reaction allows the formation of C(sp(2))-C(sp(2)) bonds through selective C(sp(2))-S bond cleavage, showcasing the new reactivity of 2-PySO2CF2H reagent. The use of readily available nickel catalyst and sulfones as coupling partners enables facile access to biaryls under mild reaction conditions without pregeneration of arylmetal reagents.
Article
Chemistry, Organic
Xia-Bin Xiang, Sheng Wang, Teng Xu, Shanshan Chen
Summary: We developed an effective Pd-catalyzed regioselective hydroesterification method for 1,3-conjugated enynes with aryl formates. Using the Pd-CyDPEphos catalytic system, the conjugated enynes reacted with phenyl formates to selectively provide 2-ester-substituted 1,3-dienes in good yields and excellent regioselectivities.
Review
Chemistry, Multidisciplinary
Jin-Bao Peng, Xin-Lian Liu, Lin Li, Xiao-Feng Wu
Summary: Carbonylation is a powerful method for the preparation of carbonylated compounds, and asymmetric carbonylation is a direct approach to constructing chiral compounds. This review summarizes recent achievements in palladium-catalyzed asymmetric carbonylation reactions.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Organic
Heng Zhang, Xiaoyan Lv, Hanrui Yu, Zibo Bai, Gong Chen, Gang He
Summary: A new protocol has been developed for amide-directed Cu-catalyzed aminoalkylation of unactivated alkenes using cyclobutanone oxime esters as alkyl radical donors. Both primary and secondary alkyl groups can be selectively installed at the C4 position of terminal or cis-internal 3-alkenamides in moderate to good yield. The use of a weakly coordinating counteranion as the Cu catalyst is critical for the formation of beta-lactam products.
Article
Chemistry, Physical
Ashis Das, Luca Buzzetti, Mikus Purins, Jerome Waser
Summary: In this study, we report an enantioselective palladium-catalyzed reaction, which utilizes a trifluoroacetaldehyde-derived tether to react with propargylic amines, generating chiral oxazolidines. Through diastereoselective hydrogenation using a heterogeneous palladium catalyst, protected benzylic amino alcohols can be obtained with yields of 45-87% and enantiomeric excess (ee) values of 84-94%. A catalytic amount of aryl iodide is required for the hydroalkoxylation of alkynes, highlighting the important role of a putative Pd(II)/ArI oxidative addition complex in promoting the oxypalladation/protodemetalation reaction.
Article
Chemistry, Physical
Xiao-Qing Han, Lei Wang, Ping Yang, Jing-Yuan Liu, Wei-Yan Xu, Chao Zheng, Ren-Xiao Liang, Shu-Li You, Junliang Zhang, Yi-Xia Jia
Summary: A palladium-catalyzed intramolecular enantioselective Mizoroki-Heck reaction of naphthalenes has been developed, leading to the formation of a series of unique heterocyclic compounds with enantiomeric excess values retained. The reaction relies on the use of a chiral sulfonamide phosphine ligand to inhibit competitive and undesired reactions.
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
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
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.