Review
Chemistry, Organic
Debasish Kundu, Atanu Mahata, Totan Roy
Summary: This article reviews the recent advances in the synthesis of aryl and heteroaryl selenides through homogeneous and heterogeneous transition metal catalyzed cross-coupling reactions and directed selenylation via CH bond activations in the past decade.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pan Pan, Shihan Liu, Yu Lan, Huiying Zeng, Chao-Jun Li
Summary: A visible-light-induced, transition-metal and photosensitizer-free cross-coupling of aryl iodides with hydrazones was developed. Hydrazones were used as alternatives to organometallic reagents, making this cross-coupling mild and green. Mechanistic investigations revealed the formation of an electron donor-acceptor complex, generating an aryl radical via single-electron transfer.
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.
Letter
Chemistry, Organic
Na-Na Ma, Xuan-Bo Hu, Yuan-Shuai Wu, Ya-Wen Zheng, Mengtao Ma, Xue-Qiang Chu, Hao Xu, Haiqing Luo, Zhi-Liang Shen
Summary: A direct cross-coupling reaction of aryl thioether with aryl bromide was successfully achieved using nickel salt, magnesium, and lithium chloride as catalysts in tetrahydrofuran solvent at room temperature. The one-pot reactions efficiently cleaved the C-S bond, yielding the desired biaryls in moderate to good yields, without the need for pregenerated or commercial organometallic reagents.
Article
Chemistry, Multidisciplinary
Quanquan Wang, Boon Chong Lee, NingXi Song, Ming Joo Koh
Summary: Stereoselective C-glycosylation reactions using bench-stable heteroaryl glycosyl sulfone donors are rare. This study presents two complementary nonprecious metal catalytic systems based on iron or nickel, capable of efficiently coupling heteroaryl glycosyl sulfones with aromatic nucleophiles or electrophiles through distinct mechanisms and modes of activation. The methods provide excellent selectivity, scope, and functional-group compatibility, allowing access to both alpha and beta isomers of key sugar residues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jin-He Na, Xiang Liu, Jia-Wen Jing, Jing Wang, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A step-economical and efficient one-pot reaction was developed for the direct cross-coupling of aryl fluorosulfate with aryl bromide. This reaction, conducted at room temperature in THF solvent, does not require the use of preprepared/commercial organometallic reagents. By utilizing nickel catalyst, magnesium turnings, and lithium chloride, the desired biaryls were obtained in moderate to good yields with reasonable functional group compatibility.
Article
Chemistry, Organic
Chenchen Li, Qi Qin, Aocong Guan, Wen Yang, Wanxiang Zhao
Summary: We present a general and efficient transition-metal-free C-C bond cross-coupling reaction of (hetero)-aryl ethers and diarylmethanes via C-(sp(2))-O bond cleavage. The coupling reactions mediated by KHMDS demonstrated high efficiency, broad substrate scope, and good functional group tolerance. The robustness and practicality of this protocol were further demonstrated by gram-scale preparation and diversified product derivatization.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiangxiang Kong, Jing Ren, Jinlong Li, Yu Liu, Kaizhi Li
Summary: A novel copper-catalyzed cross-dehydrogenative-coupling (CDC) process has been developed for the straightforward synthesis of alpha-aryl-alpha-heteroaryl alpha-amino acid scaffolds using arylglycine derivatives and N-heteroarenes. This protocol demonstrates a wide substrate scope and good functional group compatibility by utilizing air as the sole oxidant. The reaction also allows for late-stage functionalization of arylglycines bearing natural compounds or drug motifs.
Article
Chemistry, Organic
Na-Na Ma, Jing-Ao Ren, Xiang Liu, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: The direct cross-couplings of aryl sulfonium salts with aryl halides using nickel as a reaction catalyst were successfully achieved. The reactions proceeded efficiently via C-S bond activation at ambient temperature, providing moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions.
Article
Chemistry, Organic
Alec H. Christian
Summary: The metallaphotoredox-catalyzed C-S cross-coupling allows for the formation of biaryl thioethers from heteroaryl bromides and alpha-thioacetic acids. This method facilitates cross-coupling between building blocks containing reactive functional groups, nitrogen heterocycles, and pharmaceutically relevant scaffolds. Mechanistic experiments show a unique pathway for the C-S cross-coupling to occur.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Baosheng Wei, Qianyi Ren, Thomas Bein, Paul Knochel
Summary: A variety of functionalized triarylmethane and 1,1-diarylalkane derivatives were successfully synthesized via a transition-metal-free, one-pot, two-step procedure, demonstrating the synthetic utility of the method for biologically relevant molecules. The sequential cross-coupling enabled by changing the solvent from THF to toluene and the proposed S(N)1-type mechanism were supported by experimental studies. The method was further demonstrated by the synthesis of several biologically relevant molecules, including an anti-tuberculosis agent, an anti-breast cancer agent, a precursor of a sphingosine-1-phosphate (S1P) receptor modulator, and a FLAP inhibitor.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Gilian T. Thomas, Kiera Ronda, J. Scott McIndoe
Summary: The cross-coupling of N-tosylhydrazones and aryl halides to form carbon-carbon bonds, producing 1,1-disubstituted alkenes, has been widely used in chemistry, but its mechanism remains experimentally unexplored. The combination of benchtop NMR and real-time mass spectrometry allows for monitoring of catalytic intermediates and the rate of product formation.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Chen Zhang, Na-Na Ma, Zi-Lun Yu, Chuanji Shen, Xiaocong Zhou, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: The efficient palladium-catalyzed direct reductive cross-coupling reaction proceeds smoothly at room temperature with moderate to good yields, showing reasonable functional group tolerance. The one-pot reaction using readily available aryl bromide as a coupling partner is simple to handle, avoiding the use of pre-prepared organometallic reagents.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Chuntao Zhong, Mengna Liu, Xianchao Qiu, Hao Wei, Benqiang Cui, Yanhui Shi, Changsheng Cao
Summary: A nickel-catalyzed cross-coupling reaction between aryl methyl sulfides and aryl bromides has been developed to efficiently access biaryls. The method has a wide scope of substrates and is scalable, with commercially available aryl bromides being used without the need for preparation of organometallic reagents. This reaction has high application value.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Wei-Can Dai, Bo Yang, Shi-He Xu, Zhong-Xia Wang
Summary: The reaction of aryl 2-pyridyl ethers with arylzinc reagents catalyzed by NiCl2(PCy3)(2) can achieve aryl-aryl cross-coupling with a wide range of substrates and good functional group compatibility. It was found that beta-H-free alkylzinc reagents are more suitable as nucleophiles in this transformation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Guang-Li Xu, Zhong-Xia Wang
Summary: Regioselective silylation of 2,3-allenols with disilanes was achieved under the catalysis of Pd(2)dba(3)/P(o-MeOC6H4)(3). The presence of Cs2CO3 led to the formation of 2-silyl-1,3-dienes. The reaction showed different selectivities and major isomers depending on the substrate used.
Article
Chemistry, Organic
Hong Miao, Zhong-Xia Wang
Summary: A ruthenium-catalyzed oxidative cross-coupling reaction of alkenes with triisopropylsilylacetylene was achieved, directed by 2-pyridyl or 2-pyrimidyl groups. This protocol showed good compatibility with various functional groups and exhibited Z-selectivity for the enyne products.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Guang-Li Xu, Zhong-Xia Wang
Summary: Conjugated polyenes with allylic amino and hydroxy groups were successfully synthesized through the palladium-catalyzed reaction of 2,3-allenols with amines. Using MeOH as the solvent led to (Z)-configured [3]dendralene derivatives, while using iPrOH as the solvent resulted in (1Z,3E)-1,3-diene derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: This article describes the rhodium-catalyzed P(III)-directed aromatic C-H acylation reaction with amides. The reaction features a simple catalyst system, mild reaction conditions, monoacylation selectivity, a wide scope of substrates, and good compatibility of functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Guang-Li Xu, Yu-Tong Duan, Zhong-Xia Wang
Summary: In this study, the reaction of 2,3-allenols with PhMe2SiZnCl or Ph2MeSiZnCl under the catalysis of IPrCuCl or SIPrCuCl was carried out, resulting in the formation of 2-silyl-1,3-butadienes. Both secondary and tertiary 2,3-allenols could be used as coupling partners. The reaction of secondary 2,3-allenols exclusively gave (E)-2-silyl-1,3-butadienes as the products.
Article
Chemistry, Applied
Xue-Yi He, Zhong-Xia Wang
Summary: The ruthenium(II)-catalyzed reaction between aniline derivatives and allylamines was used to synthesize 2-methylindoles via C-H/C-N bond activation. The most effective directing group is the 4,5-dimethyl pyrimidin-2-yl group attached on the nitrogen atom of anilines, while N-allyl-4-fluoro-N-methylaniline is the optimal allylamine. The cyclization products were obtained in yields ranging from 16% to 96%. The reaction does not require an external oxidant, and a possible mechanism is proposed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Bo Yang, Jihui Gao, Xingfa Tan, Yicong Ge, Chuan He
Summary: A new type of chiral silyl ligand is developed, enabling the first iridium-catalyzed atroposelective intermolecular C-H silylation reaction of 2-arylisoquinolines. This protocol offers mild reaction conditions, high atom economy, and remarkable yield with excellent stereoselectivity, delivering enantioenriched axially chiral silane platform molecules with facile convertibility. The success of this unprecedented transformation relies on a novel chiral PSiSi-ligand, which facilitates the intermolecular C-H silylation process with perfect chem-, regio-, and stereo-control via a multi-coordinated silyl iridium complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: The [Ru(p-cymene)Cl-2](2)-catalyzed reaction of 2-arylpyridines with 1-aryl-2-vinylpyrrolidines in CF3CH2OH at 40 ? in the presence of KOAc affords ortho-C-H allylation products of arenes with high yields and Z/E ratios. The protocol is applicable to a wide range of substrates and tolerates various functional groups including alkyl, aryl, MeO, F, Cl, Br, OCF3, and CF3 groups.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: Alkyl aryl ketones were synthesized through a nickel-catalyzed reductive coupling reaction of arylcarboxylic acid (2-pyridyl)esters with alkyl methanesulfonates, both primary and secondary, under mild conditions. This methodology is compatible with various substrates and functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Yu-Tong Duan, Zhong-Xia Wang
Summary: The ruthenium-catalyzed reaction of aryl methyl thioethers with vinylaziridines provides ortho-position mono- or bis-allylation products, depending on the substituents on the phenyl rings of sulfide substrates or the ratio of reactants. This reaction exhibits mild conditions, high product yields, a broad range of substrates, good compatibility of functional groups, and selective formation of E-configurated C-C double bonds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Anrong Chen, Bo Yang, Zhenghong Zhou, Feng Zhu
Summary: Chemical synthesis is an effective strategy for carbohydrate synthesis, allowing precise control of sugar chain structure. Researchers have focused on developing stereoselective glycosylation to access carbohydrate mimics, resulting in remarkable progress. Transition-metal-catalyzed glycosylation reactions have emerged as a powerful tool for the synthesis of various glycosides and glycoconjugates due to their versatility, efficiency, and stereoselectivity.
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: The nickel-catalyzed cross-electrophile coupling of aryl chlorides with allylic alcohols proceeds efficiently under mild conditions in the presence of zinc powder and MgCl2 to produce allylarenes in moderate to high yields. The reaction exhibits high regioselectivity and E/Z-selectivity, particularly when 1- or 3-arylallyl alcohols are used as substrates. Various functional groups and nitrogen-containing heterocycles are tolerated in the reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xue-Yi He, Zhong-Xia Wang
Summary: The synthesis of 1,4-enynes via nickel-catalyzed cross-coupling of allylic alcohols with alkynylzinc reagents exhibits high regio- and E/Z-selectivity, especially when aryl-substituted allylic alcohols are employed. The method also shows a wide scope of substrates and good compatibility of functional groups.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Wei-Ze Li, Zhong-Xia Wang
Summary: The Ni(PEt3)Cl-2-catalyzed silylation of alkyl aryl sulfoxides with silylzinc reagents allows for the conversion to arylsilicon compounds under mild reaction conditions, with tolerance to a variety of functional groups and a wide scope of substrates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
