Article
Chemistry, Applied
Jing-Ao Ren, Xue Chen, Chao Gui, Chengping Miao, Xue-Qiang Chu, Hao Xu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: A step-economical and operationally simple nickel-catalyzed cross-electrophile coupling reaction was developed, enabling the coupling of aryl phosphates and aryl bromides through C-O bond cleavage without the use of moisture-labile and uncommonly available organometallics. The reaction proceeded smoothly in the presence of magnesium turnings and lithium chloride in THF solvent, providing moderate to good yields of biaryls with reasonable functionality tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Baojian Xiong, Yue Li, Jinyu Zhang, Jiangjun Liu, Xuemei Zhang, Zhong Lian
Summary: A dual nickel-/palladium-catalyzed direct gem-difluorovinylation method has been developed for the synthesis of diverse difluoroalkene compounds under mild reaction conditions, offering a potential pathway for the late-stage functionalization of complex bioactive molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Linlin Ding, Yue Zhao, Hongjian Lu, Zhuangzhi Shi, Minyan Wang
Summary: For the first time, a catalytic enantioselective propargyl-aryl cross-coupling between two electrophiles was achieved in a stereoconvergent manner. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Physical
Quan Lin, Guobin Ma, Hegui Gong
Summary: A new method was developed for direct coupling of unactivated alcohols with aryl halides through in situ halogenation/reductive coupling, forming Csp2-Csp3 bonds. This method enables rapid transformation of a wide range of alcohols to their bromide counterparts, suitable for arylation of complex alcohols without the need for prepreparation of alkyl halides.
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
Kai Kang, Nathan L. Loud, Tarah A. DiBenedetto, Daniel J. Weix
Summary: A new, general approach to biheteroaryls through Ni- and Pd-catalyzed multimetallic cross-Ullmann coupling has been developed, demonstrating successful synthesis of a variety of heteroaryl halides and triflates. This method showed high generality and >90% hit rate in a 96-well plate format.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Guoqing Yang, Yanwei Wang, Youai Qiu
Summary: A nickela-electrocatalyzed cross-electrophile coupling of aryl aziridines and aryl bromides has been developed to access synthetic useful beta-arylethylamines under mild and sustainable electrochemical conditions. This protocol exhibits excellent chemo- and regioselectivity, broad substrate scope, and good functional group compatibility. Mechanistic studies have confirmed that the observed regioselectivity and reactivity are due to the electro-induced ring-opening of aziridines to generate a benzyl radical intermediate as the active species. Furthermore, this strategy enables the cross-coupling with CO2 to access beta-amino acids under mild conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Zhaodong Zhu, Yuxin Gong, Weiqi Tong, Weichao Xue, Hegui Gong
Summary: A nickel-catalyzed reductive coupling of aryl triflates with thiocarbonates was reported, showing compatibility with various aryl C(sp(2))-O electrophiles and O-tBu S-alkyl thiocarbonates. The reaction demonstrated good chemoselectivity in cleaving C-O bonds compared to thioesters. This work expands the scope of nickel-catalyzed reductive cross-electrophile coupling reactions.
Article
Chemistry, Physical
Gang Chen, Ruoxin Zhou, Xuemei Zhang, Xue Xiao, Soren Kramer, Gui-Juan Cheng, Zhong Lian
Summary: This article reports a carbonylative cross-electrophile coupling reaction that utilizes carbon monoxide gas as both the carbonyl source and reductant. The use of Pd/Rh cooperative catalysis enables the carbonylation coupling of easily accessible aryl triflates and aryl bromides.
Article
Chemistry, Physical
Jiantao Fu, Windsor Lundy, Rajdip Chowdhury, J. Cameron Twitty, Long P. Dinh, Jessica Sampson, Yu-hong Lam, Christo S. Sevov, Mary P. Watson, Dipannita Kalyani
Summary: An electrochemical, nickel-catalyzed reductive coupling between alkylpyridinium salts and aryl halides is described. High-throughput experimentation (HTE) was used for rapid optimization and evaluation of various pharmaceutically relevant aryl halides, including complex drug-like substrates. The transformation is compatible with both primary and secondary alkylpyridinium salts with different conditions. Mechanistic insights were crucial for improving the efficiency of coupling using secondary alkylpyridinium salts. Systematic comparisons between electrochemical and non-electrochemical methods revealed the complementary scope and efficiency of the two approaches.
Article
Chemistry, Physical
Bijan Mirabi, Austin D. Marchese, Mark Lautens
Summary: In this study, a nickel-catalyzed cross-electrophile coupling reaction of aryl chlorides and heteroaryl chlorides was reported, enabled by a synergistic combination of halide effects and the addition of a magnesium salt. Electronic-deficient aryl chlorides were found to perform the best in the reaction, and preliminary mechanistic evidence showed that MgCl2 is crucial for accelerating the reduction of Ni(II) while small quantities of iodide lead to improved yields.
Article
Chemistry, Multidisciplinary
Lorenzo Lombardi, Alessandro Cerveri, Riccardo Giovanelli, Marta Castineira Reis, Carlos Silva Lopez, Giulio Bertuzzi, Marco Bandini
Summary: This paper presents a nickel-catalyzed reductive cross-electrophile coupling reaction, which achieves high yields and high functional group tolerance in the arylation of trifluoroacetaldehyde through a solvent-assisted 1,2-Hydrogen Atom Transfer (HAT) process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shi Tang, Zhen-Hua Xu, Ting Liu, Shuo-Wen Wang, Jian Yu, Jian Liu, Yu Hong, Shi-Lu Chen, Jin He, Jin-Heng Li
Summary: A novel nickel-catalyzed radical relay has been reported for the remote cross-electrophile coupling of amino acid esters with aryl bromides, enabling the formation of two new C(sp(3))-C(sp(2)) bonds with broad substrate scope and excellent diastereoselectivity. Mechanistically, this cascade reaction combines powerful catalytic cycles involving cross-electrophile coupling and radical aryl migration, resulting in the generation of C(sp(3))-centered radical intermediates and the transformation of transient alkyl radical into a robust alpha-aminoalkyl radical.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sii Hong Lau, Meredith A. Borden, Talia J. Steiman, Lucy S. Wang, Marvin Parasram, Abigail G. Doyle
Summary: This study introduces a Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides, yielding enantioenriched 2,2-diarylalcohols. Analysis shows that enantioselectivity is correlated with the electronic properties of the ligands, with more electron-donating ligands leading to higher ee values. Experimental and computational studies support the hypothesis that reductive elimination is enantiodetermining and ligand electronic properties affect enantioselectivity by altering the position of the transition state structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Kai Kang, Shuanshuan Liu, Ting Xu, Decai Wang, Xuebing Leng, Ruopeng Bai, Yu Lan, Qilong Shen
Article
Chemistry, Organic
Kai Kang, Chunfa Xu, Qilong Shen
ORGANIC CHEMISTRY FRONTIERS
(2014)
Article
Chemistry, Inorganic & Nuclear
Shuanshuan Liu, Kai Kang, Shihan Liu, Decai Wang, Ping Wei, Yu Lan, Qilong Shen
Article
Chemistry, Multidisciplinary
Liangbin Huang, Laura K. G. Ackerman, Kai Kang, Astrid M. Parsons, Daniel J. Weix
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Inorganic & Nuclear
Kai Kang, Shihan Liu, Chunhui Xu, Zehai Lu, Shuanshuan Liu, Xuebing Leng, Yu Lan, Qilong Shen
Summary: Investigation into the C(sp(2))-X reductive eliminations of a series of halogenated organogold(III) complexes revealed that the process occurs synchronously via a three-membered transition state.
Article
Chemistry, Multidisciplinary
Kai Kang, Nathan L. Loud, Tarah A. DiBenedetto, Daniel J. Weix
Summary: A new, general approach to biheteroaryls through Ni- and Pd-catalyzed multimetallic cross-Ullmann coupling has been developed, demonstrating successful synthesis of a variety of heteroaryl halides and triflates. This method showed high generality and >90% hit rate in a 96-well plate format.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Kai Kang, Daniel J. Weix
Summary: This study successfully develops a two-step, one-pot protocol for the in situ generation of N-hydroxyphthalimide esters and their nickel-catalyzed cross-electrophile coupling with unactivated alkyl bromides, enabling the construction of C(sp3)-C(sp3) bonds. The conditions tolerate various functional groups, and mechanistic studies demonstrate the conversion of both substrates to alkyl radicals during the reaction.
Article
Chemistry, Physical
Changhui Lu, Yueping Lin, Minyan Wang, Jiaming Zhou, Shuo Wang, Huanfeng Jiang, Kai Kang, Liangbin Huang
Summary: In this study, a nickel-catalyzed ring-opening transformation of benzofuran with silanes was reported, selectively giving ortho-alkene-, branched/linear alkyl silane-, and alkenyl silane-substituted phenol derivatives. This reaction provides a highly desirable and underdeveloped method for the construction of valuable phenol derivatives.
Article
Chemistry, Multidisciplinary
Zhi-Ming Su, Jack Twilton, Caroline B. Hoyt, Fei Wang, Lisa Stanley, Heather B. Mayes, Kai Kang, Daniel J. Weix, Gregg T. Beckham, Shannon S. Stahl
Summary: Lignin-derived aromatic chemicals are considered as potential substitutes for petrochemical feedstocks, and their applications in producing biobased, less toxic alternatives to phthalate plasticizers are extensively studied. In this study, 4-Hydroxybenzoic acid (H), vanillic acid (G), and syringic acid (S) were used to synthesize biaryl dicarboxylate esters through catalytic reductive coupling methods. New catalysts were discovered to achieve the challenging cross-coupling products, and high-throughput experimentation and electrochemical methods were utilized for catalyst screening and yield improvement. The performance of the resulting esters in poly(vinyl chloride) plasticizers was evaluated, and the H-G and G-G derivatives showed advantages over petroleum-based phthalate ester plasticizers.
ACS CENTRAL SCIENCE
(2023)
