Article
Chemistry, Physical
Zhiyang Lin, Weitao Hu, Linchuan Zhang, Chuan Wang
Summary: In this study, we describe a nickel-catalyzed asymmetric three-component trans-dicarbofunctionalization reaction of beta-substituted alpha-naphthyl propargylic alcohols using aryl and benzyl halides as coupling partners under reductive conditions. This cross-electrophile strategy allows for the synthesis of various axially chiral allylic alcohols with complete regio- and E-selectivity, as well as high enantiocontrol. By utilizing the hydroxyl group as a functional handle, these structural motifs can be successfully derivatized into diverse functional group-rich axially chiral alkenes.
Article
Chemistry, Multidisciplinary
Lingxiang Lu, Yi Wang, Wendy Zhang, Wen Zhang, Kimberly A. See, Song Lin
Summary: The cross-electrophile dialkylation of alkenes allows for regioselective dialkylation of alkenes without the use of transition-metal catalysts, leading to the formation of two C-(sp(3))-C-(sp(3)) bonds. This method provides a modular and efficient approach to building structural complexity in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Kirsten A. Hewitt, Claire A. Herbert, Elizabeth R. Jarvo
Summary: A nickel-catalyzed intramolecular conjunctive cross-electrophile coupling reaction has been developed for the synthesis of 3,5-vicinal carbocyclic rings found in various biologically active compounds and natural products. Mechanistic experiments suggest that the reaction proceeds through alkyl iodides formed in situ, initiates at the secondary electrophilic center, and proceeds via radical intermediates.
Article
Chemistry, Organic
Kangning Cao, Zhan-Ming Zhang, Junliang Zhang, Fener Chen
Summary: The study presents a highly selective Pd-catalyzed reaction for the synthesis of a series of chiral benzene-fused cyclic compounds in a convenient manner.
Article
Chemistry, Physical
Fang Wang, Shiwei Pan, Shengqing Zhu, Lingling Chu
Summary: A novel Ni-catalyzed enantioselective reductive three-component alkylalkenylation reaction is reported, which shows high conversion and broad substrate scope for various alkenes.
Article
Chemistry, Multidisciplinary
Madeline E. Rotella, Dinabandhu Sar, Lei Liu, Osvaldo Gutierrez
Summary: The study describes an iron-catalyzed regioselective dicarbofunctionalization of electron-rich alkenes using aryl- and alkyl vinyl ethers as effective linchpins to couple alkyl or (fluoro)alkyl halides and sp(2)-hybridized Grignard nucleophiles. Preliminary results demonstrate the ability to engage thioethers as linchpins and control enantioselectivity in these transformations, an area which is largely unexplored in iron-catalyzed three-component cross-coupling reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ming-Xiang You, Pei-Feng Su, Ze-Hui She, Xing-Zhong Shu
Summary: The C-Ge cross-coupling is a promising method for the precise synthesis of organogermanes. This study demonstrates the possibility of converting low-cost and easily available ester groups into organogermanes through cleavage of stable C-O bonds. The coupling of primary, secondary, and even tertiary benzylic pivalates with chlorogermanes is achieved under mild conditions. The scalability of the reaction and the derivatization of the formed benzylgermanes are also demonstrated.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jie Sheng, Hui-Qi Ni, Shan-Xiu Ni, Yan He, Ru Cui, Guang-Xu Liao, Kang-Jie Bian, Bing-Bing Wu, Xi-Sheng Wang
Summary: Monofluorinated alkyl compounds play a significant role in pharmaceuticals, agrochemicals, and materials. This study demonstrates a direct nickel-catalyzed monofluoromethylation of unactivated alkyl halides using a cost-effective industrial raw material, bromofluoromethane, showing high efficiency, mild conditions, and excellent functional-group compatibility. The research establishes a new method for the synthesis of aliphatic fluorides through reductive cross-coupling of alkyl halides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Angel Renteria-Gomez, Macayla Guerrero, Mireya Ramirez-Lopez, Osvaldo Gutierrez
Summary: Fluoroalkylated compounds play significant roles in various fields, and the dicarbofunctionalization of alkenes is an efficient method for rapid compound construction and diversification. This study presents the first iron-catalyzed three-component fluoroalkylarylation of enamides, using selective formation and trapping of radicals under mild conditions and fast reaction times, providing an efficient synthetic route to build molecular complexity.
Article
Chemistry, Multidisciplinary
Nate W. J. Ang, Lutz Ackermann
Summary: In this research, an efficient and mild electrochemical thiolation method was developed for the synthesis of alkyl sulfides by cross-electrophile coupling of alkyl bromides with bench-stable thiosulfonates. Mechanistic insights into this electrocatalytic thiolation reaction were elucidated through cyclic voltammetry and potentiostatic analysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yue Min, Jie Sheng, Jian-Liang Yu, Shan-Xiu Ni, Guobin Ma, Hegui Gong, Xi-Sheng Wang
Summary: A nickel-catalyzed asymmetric trifluoroalkylation of aryl iodides was described for the first time, demonstrating high efficiency, mild conditions, and excellent functional group tolerance, especially for substrates containing diverse pharmaceutical and bioactive molecules moieties. This strategy provided an efficient and facile way for diversity-oriented synthesis of chiral trifluoromethylated alkanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Connor M. Simon, Samantha L. Dudra, Ryan T. McGuire, Michael J. Ferguson, Erin R. Johnson, Mark Stradiotto
Summary: This study reveals a new reductive elimination pathway for nickel-catalyzed C-N cross-coupling, involving a bifurcated pathway and a base-promoted pathway for C-N reductive elimination.
Article
Chemistry, Physical
Decai Ding, Linchuan Zhang, Hao Wen, Chuan Wang
Summary: Here, a cobalt-catalyzed asymmetric reductive 1,2-dicarbofunctionalization of 1,3-dienes using obromoaryl imines as a bis-electrophilic coupling partner is reported. This method provides a pathway to prepare disubstituted cis-indanes in high diastereo- and enantioselectivities under mild reaction conditions. The proposed reaction mechanism includes enantioselective intermolecular migratory insertion and diastereoselective intramolecular allylation as the key elementary steps.
Article
Multidisciplinary Sciences
Wen Zhang, Lingxiang Lu, Wendy Zhang, Yi Wang, Skyler D. Ware, Jose Mondragon, Jonas Rein, Neil Strotman, Dan Lehnherr, Kimberly A. See, Song Lin
Summary: Recent research in medicinal chemistry has found a correlation between an increase in sp(3) carbons in drug candidates and their improved success rate in clinical trials. This study focuses on the development of robust and selective methods for constructing carbon(sp(3))-carbon(sp(3)) bonds. By using electrochemistry, the researchers achieve the selective activation of alkyl halides based on their electronic and steric properties, allowing for high selectivity in carbon(sp(3))-carbon(sp(3)) cross-electrophile coupling. This new protocol shows improved chemoselectivity and does not require a transition metal catalyst.
Article
Chemistry, Multidisciplinary
Takeshi Fujita, Yutaro Kobayashi, Ikko Takahashi, Ryutaro Morioka, Tomohiro Ichitsuka, Junji Ichikawa
Summary: Nickel-catalyzed reductive cross-coupling of allylic difluorides with aryl iodides was successfully achieved, leading to the synthesis of a series of gamma-arylated monofluoroalkenes with moderate to high yields and high Z-selectivities. Mechanistic studies indicated that the cleavage of C-I bonds in aryl iodides and C-F bonds in allylic difluorides occurred through oxidative addition and beta-fluorine elimination, respectively.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xiantang Li, Yujia Mao, Pei Fan, Chuan Wang
Summary: We have developed a nickel/TBADT cocatalyzed acyl C-H benzylation method, which allows for the synthesis of various ketones under mild reaction conditions. This protocol provides a convenient and efficient approach in synthetic chemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chang Zhang, Lin Wang, Hongzhang Shi, Zhiyang Lin, Chuan Wang
Summary: Iron is shown to efficiently catalyze a reaction between alpha-trifluoromethyl alkenes and unactivated ketones, resulting in the synthesis of diverse functional-group-rich compounds. This operation is simple and does not require pre-generated organometallics.
Article
Chemistry, Physical
Bing Yuan, Decai Ding, Chuan Wang
Summary: In this study, we have successfully implemented a reductive strategy for the ring opening reaction of aryl cyclopropylketones with unactivated alkyl bromides. The nickel-catalyzed reductive Csp3-Csp3cross-coupling reaction proceeds with complete regioselectivity, bypassing the need for pregenerated organometallics and allowing for efficient synthesis of alkylated ketones with high step economy and functionality tolerance.
Article
Chemistry, Organic
Weitao Hu, Zhiyang Lin, Chuan Wang
Summary: Here, we describe a nickel-catalyzed cross-electrophile ring-opening reaction of vinyl epoxides, where aryl iodides, alkyl iodides, and benzyl chlorides can all be used as electrophilic coupling partners, providing a new approach to preparing multisubstituted allylic alcohols. This method exhibits broad substrate scope, good step-economy, high selectivity, and mild reaction conditions.
Article
Chemistry, Physical
Chuan Wang, Rui Wang, Pei Fan
Summary: We developed a highly enantioselective acyl C-H allylation reaction, which can synthesize highly enantioselective α-stereogenic β,γ-unsaturated 1,4-dicarbonyl compounds.
Article
Chemistry, Physical
Decai Ding, Linchuan Zhang, Hao Wen, Chuan Wang
Summary: Here, a cobalt-catalyzed asymmetric reductive 1,2-dicarbofunctionalization of 1,3-dienes using obromoaryl imines as a bis-electrophilic coupling partner is reported. This method provides a pathway to prepare disubstituted cis-indanes in high diastereo- and enantioselectivities under mild reaction conditions. The proposed reaction mechanism includes enantioselective intermolecular migratory insertion and diastereoselective intramolecular allylation as the key elementary steps.
Article
Chemistry, Multidisciplinary
Decai Ding, Bing Yuan, Hao Wen, Chuan Wang
Summary: Asymmetric ring opening (ARO) is a powerful tool for constructing chiral cyclic molecules with multiple stereocenters. In this article, the strategy of cross-electrophile coupling is successfully applied to the ARO reaction of oxa- and azabicyclic alkenes. By using functionalized alkyl bromides as coupling partners, highly enantioenriched 1,2-dihydronaphthalenes with full cis-selectivity can be efficiently synthesized under the catalysis of a chiral nickel complex.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jiawei Liu, Wei Tang, Chuan Wang
Summary: Here, we report a nickel-catalyzed regio- and enantioselective ring opening reaction of 3,4-epoxy amides and esters with aromatic amines as nucleophiles. This method demonstrates high regiocontrol, diastereospecific S(N)2 reaction pathway, broad substrate scope, and mild reaction conditions, enabling the synthesis of a wide range of gamma-amino acid derivatives in a highly enantioselective manner. Notably, the selective nucleophilic attack to the C-4 position of epoxides is controlled by the directing effect of the pendant carbonyl group.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Letter
Chemistry, Organic
Bing Yuan, Chang Zhang, Haiyan Dong, Chuan Wang
Summary: By merging C-C and C-F bond cleavage, a regioselective ring opening/gem-difluoroallylation of cyclopropyl ketones with a-trifluoromethylstyrenes was developed, which proceeds under the catalysis of iron with the combination of manganese and TMSCl as the reducing agents. This reaction provides a new entry to the synthesis of carbonyl-containing gem-difluoroalkenes. Remarkably, the ketyl radical-induced selective C-C bond cleavage and the following generation of more-stable carbon-centered radicals enable complete regiocontrol of this ring opening reaction for various substitution patterns of the cyclopropane ring.
Article
Chemistry, Organic
Hao Wen, Decai Ding, Chuan Wang
Summary: In this study, a nickel-catalyzed diastereoselective cross-electrophile ring opening reaction was developed using aromatic aldehydes as the electrophilic coupling partner and Zn as the stoichiometric reductant. This reaction successfully achieved the formation of two disubstituted sp3-hybridized carbon centers, resulting in a variety of 1,2-dihydronaphthalenes with full diastereocontrol of three consecutive stereogenic centers.
Article
Chemistry, Organic
Hongqing Yao, Chuan Wang
Summary: Here, the authors present a yttrium-catalyzed regioselective ring-opening reaction between 2,3-epoxy esters and amides with amines as nucleophiles. This method offers high regiocontrol, an enantiospecific S(N)2 reaction pathway, a wide substrate scope, and mild reaction conditions, resulting in the synthesis of a broad range of regioisomerically pure alpha-hydroxy beta-amino esters and amides. Importantly, the selective nucleophilic attack at the C-3 position is controlled by the directing effect of the carbonyl group of the substrates.
Article
Chemistry, Organic
Feiyan Yang, Chuan Wang
Summary: In this study, we employ polycyclic aryl-activated alkyl ammonium triflates as the electrophilic aryl-activated alkylating agent in the nickel-catalyzed hydroxyl- or sulfonamide-directed cross-electrophile coupling reaction with phenyl benzoates, resulting in the synthesis of diverse aryl ketones under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rui Wang, Chuan Wang
Summary: By combining nickel-mediated aza-Heck cyclization and radical acyl C-H activation, a highly enantioselective imino-acylation of oxime ester-tethered alkenes with aldehydes was achieved using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst. The reaction provides a convenient route to synthesize enantioenriched pyrrolines bearing an acyl-substituted stereogenic center under mild conditions. Preliminary mechanistic studies indicate a Ni(i)/Ni(ii)/Ni(iii) catalytic sequence involving intramolecular migratory insertion of a tethered olefin into the Ni(iii)-N bond as the enantiodiscriminating step.
Article
Chemistry, Organic
Hao Wen, Decai Ding, Chuan Wang
Summary: In this study, a nickel-catalyzed diastereoselective cross-electrophile ring opening reaction of 7-oxabenzonorbornadienes with aromatic aldehydes was developed, using Zn as the stoichiometric reductant. This reaction achieved stereoselective bond formation between two disubstituted sp(3)-hybridized carbon centers, providing a variety of 1,2-dihydronaphthalenes with full diastereocontrol of three consecutive stereogenic centers.
Article
Chemistry, Organic
Hongzhang Shi, Haiyan Dong, Chuan Wang
Summary: A chromium-catalyzed reductive allylic defluorinative acylation of trifluoromethyl-substituted alkenes with acyl oxime esters has been developed, allowing for efficient synthesis of various ketones bearing a gem-difluoroalkene unit.
ORGANIC CHEMISTRY FRONTIERS
(2023)