Article
Chemistry, Organic
Regina M. Oechsner, Ivo H. Lindenmaier, Ivana Fleischer
Summary: We present a nickel catalyzed C-S cross-coupling reaction of aryl and alkenyl triflates with alkyl thiols. By using an air-stable nickel precatalyst, various thioethers could be synthesized under mild reaction conditions within a short reaction time. The reaction demonstrated a broad substrate scope, including pharmaceutically relevant compounds.
Article
Chemistry, Multidisciplinary
Xingxing Ma, Luo Li, Mengwei Tan, Zihao Zhong, Jinchao Liang, Puhui Li, Qiuling Song
Summary: Four migration reactions from alkynyl tetracoordinate boron species were reported, leading to the synthesis of tetrasubstituted alkenyl monohalides. This provides a new approach for the preparation of versatile tetrasubstituted olefins.
Article
Chemistry, Multidisciplinary
Raymond F. Turro, Julie L. H. Wahlman, Z. Jaron Tong, Xiahe Chen, Miao Yang, Emily P. Chen, Xin Hong, Ryan G. Hadt, K. N. Houk, Yun-Fang Yang, Sarah E. Reisman
Summary: Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of N-hydroxyphthalimide (NHP) esters and benzylic chlorides were conducted. The study revealed divergent mechanisms for these related transformations, with the mechanism of C(sp(3)) activation changing depending on the reactants used. Kinetic experiments showed that the rate of NHP ester reduction can be tuned by changing the Lewis acid. Spectroscopic studies and DFT calculations provided insights into the catalyst resting state and the origin of enantioinduction for the Ni-BOX catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xia Hu, Ivan Cheng-Sanchez, Sergio Cuesta-Galisteo, Cristina Nevado
Summary: An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling reaction was developed for the synthesis of enantioenriched beta-aryl homoallylic amines with excellent E-selectivity. This reaction proceeds under mild conditions without the use of heterogeneous metal reductants and sacrificial anodes, employing constant current electrolysis with triethylamine as a terminal reductant. The reaction demonstrates remarkable stereocontrol, broad substrate scope, and excellent functional group compatibility, making it suitable for the late-stage modification of bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yanling Zhang, Zhiguo Zhang, Yuanyuan Hu, Yunkui Liu, Hongwei Jin, Bingwei Zhou
Summary: We have described a nickel-catalyzed cyanation reaction of aryl/alkenyl halides with alkyl isocyanides. Aryl/alkenyl iodines and bromides were found to be competent electrophiles that reacted with alkyl isocyanides to afford nitrile compounds in moderate to good yields. This protocol features broad functional group tolerance, simple reaction conditions, and gram-scale synthesis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jian-Xing Liang, Peng-Fei Yang, Wei Shu
Summary: In this study, a nickel-catalyzed Finkelstein reaction under mild conditions was reported, which can convert a wide range of aryl/alkenyl bromides as well as chlorides into corresponding iodides with broad functional group tolerance.
Article
Chemistry, Organic
Roman Kleinmans, Omar Apolinar, Joseph Derosa, Malkanthi K. Karunananda, Zi-Qi Li, Van T. Tran, Steven R. Wisniewski, Keary M. Engle
Summary: A nickel-catalyzed 1,2-diarylation of alkenyl ketones with aryl iodides and arylboronic esters has been reported, offering high levels of regiocontrol using ketones with a variety of substituents as effective directing groups. The representative product can be diversified into a wide range of useful products that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the substrate binding mode, and Hammett analysis reveals the impact of electronic factors on initial rates.
Article
Chemistry, Multidisciplinary
Shengyang Ni, Jiyao Yan, Srija Tewari, Edward J. Reijerse, Tobias Ritter, Josep Cornella
Summary: Here, a regioselective, late-stage two-step arene halogenation method is introduced. The unusual Ni(I)/(III) catalysis is achieved through the combination of aryl thianthrenium and Ni redox properties, which has not been achieved with other (pseudo)halides. The catalyst is generated in situ from inexpensive NiCl2 center dot 6(H2O) and zinc without the need for supporting ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Zi-Hao Chen, Rui-Ze Sun, Fei Yao, Xu-Dong Hu, Long-Xue Xiang, Hengjiang Cong, Wen-Bo Liu
Summary: The study presents an enantioselective nickel-catalyzed intramolecular reductive cross-coupling reaction to assemble CN-containing all-carbon quaternary stereocenters by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of an organic reductant is crucial for the selectivity and reactivity, with demonstrated applications in the synthesis of bioactive molecules and natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yipin Zhang, Xia Ge, Hongjian Lu, Guigen Li
Summary: Transition-metal-catalyzed sp(2) C-N bond formation is a reliable method for synthesizing aryl amines. This method introduces a cascade approach using organic carboxylic acids and easily prepared azidoformates as carbon and nitrogen sources, achieving high yields and minimal byproducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Claire Dejardin, Amaury Renou, Jacques Maddaluno, Muriel Durandetti
Summary: An intramolecular carbometallation of a triple bond promoted by electrochemistry and mediated by nickel catalysis is described. This domino process transforms various aryl halides bearing a propargyl chain into substituted heterocycles in one single operation, with high stereoselectivities and in good to high yields. This reaction follows a syn-exo-dig cyclization process and produces vinylbenzofuranes suitable for cycloaddition reactions at 80 degrees C.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ryota Isshiki, Miki B. Kurosawa, Kei Muto, Junichiro Yamaguchi
Summary: A Ni-catalyzed aryl sulfide synthesis method was developed using 2-pyridyl sulfide as the sulfide donor, eliminating the need for odorous and toxic thiols. The Ni/dcypt catalyst played a crucial role in the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, with mechanistic studies showing its ability to undergo oxidative additions and ligand exchanges simultaneously.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Fei Li, Weikang Xiong, Geyang Song, Yonggang Yan, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A general and efficient photochemical C-N coupling method for (hetero)aryl chlorides with hydrazides is presented. The reaction is catalyzed by a Ni(II)-bipyridine complex and does not require an external photosensitizer, making it highly practical. This method demonstrates a wide substrate scope (54 examples) and excellent functional group tolerance, and has been successfully applied to the synthesis of rizatriptan.
Article
Chemistry, Multidisciplinary
Tianhua Tang, Avijit Hazra, Daniel S. Min, Wendy L. Williams, Eli Jones, Abigail G. Doyle, Matthew S. Sigman
Summary: In this study, the oxidative addition process of Ni(I) with aryl iodides was investigated using electroanalytical and statistical modeling techniques. Essential electronic and steric factors influencing the addition rate were identified through multivariate linear regression models based on over 200 experimental rate measurements. The mechanisms of oxidative addition were classified into three-center concerted or halogen-atom abstraction pathways based on the ligand type. A global heat map of predicted oxidative addition rates was created, which was shown to be applicable in understanding the reaction outcome in a Ni-catalyzed coupling reaction through a case study.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Guo-Qin Hu, Wen-Yan Zhang, Yong-Xin Liu, Jing-Hui Liu, Bin Zhao
Summary: Here, we present a decarboxylative thiocarbonylation method of aryl and alkenyl sulfonium salts using oxalic acid monothioethers (OAMs) under visible light-accelerated palladium catalysis. The reaction demonstrates a new application of visible light-accelerated palladium catalysis in catalytic decarboxylative cross-couplings, allowing the synthesis of different types of thioester compounds. Both sulfonium salts and OAMs are easily accessible and stored reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
