Article
Chemistry, Organic
Quentin D. Tercenio, Erik J. Alexanian
Summary: The nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates reported in this study delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system, consisting of a simple nickel salt and a commercially available reductant, represents a rare example of a cross-coupling involving the C-O bonds of two electrophiles.
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Jian-Xin Zhang, Bi-Hong Chen, Wei Shu
Summary: This study reports an enantio-selective alkyl-alkyl cross-coupling reaction using a newly-developed chiral tridentate ligand. Two different alkyl halides were successfully cross-coupled to form α-tertiary aliphatic amides. The mechanism investigation revealed that one alkyl halide undergoes oxidative addition with nickel, while the other alkyl halide forms alkyl zinc reagents in situ, enabling reductive alkyl-alkyl cross-coupling without preformation of organometallic reagents.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ruofei Cheng, Graham de Ruiter, Chao-Jun Li
Summary: Cobalt-based catalysts have shown unique advantages in cross-coupling reactions, with higher catalytic activity and lower toxicity compared to palladium and nickel catalysts. A novel cobalt-catalyzed alkyl-alkyl cross-coupling reaction of hydrazone with alkyl halides has been developed under mild reaction conditions, using a PNP-type pincer ligand as an essential catalyst. Both aldehyde and ketone hydrazones are compatible with this reaction, producing a series of C(sp(3))-C(sp(3)) coupling products in moderate to good yields.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Giuseppe Dilauro, Francesco Messa, Fabio Bona, Serena Perrone, Antonio Salomone
Summary: A simple cobalt complex, Co(phen)Cl₂, has been found to be a highly efficient and cost-effective precatalyst for various cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl, and alkyl bromides. New C(sp²)-C(sp²) and C(sp²)-C(sp³) bonds can be formed in good to excellent yields and high chemoselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Kaluvu Balaraman, Christian Wolf
Summary: The Suzuki cross-coupling of benzylic and unactivated aliphatic fluorides with aryl- and alkenylboronic acids has been successfully achieved through mechanistically distinct Pd and Ni catalyzed pathways, demonstrating superiority over competing reactions in over 20 examples. The potential utility of this method is showcased in various compounds, including heterocyclic structures, 1,1-disubstituted and trans-1,2-disubstituted alkenes.
Letter
Chemistry, Organic
Panchi Guo, Hao Jin, Jinhui Han, Liang Xu, Pengfei Li, Miao Zhan
Summary: This study demonstrates a nickel-catalyzed Negishi cross-coupling reaction for the synthesis of versatile organoboron products with high functional-group tolerance. The reaction allows for the coupling of unactivated tertiary alkyl electrophiles with boron-stabilized organozinc reagents. The importance of the Bpin group in accessing the quaternary carbon center is highlighted, and the practicality of the prepared quaternary organoboronates is showcased through their conversion to other useful compounds.
Article
Chemistry, Organic
Bryan C. Figula, D. Lucas Kane, Kaluvu Balaraman, Christian Wolf
Summary: Cross-coupling of alkyl fluorides and organocuprates is achieved via aluminum halide mediated C-F bond activation, leading to the formation of Csp2-Csp3 and Csp3-Csp3 bonds. The reaction exhibits mild conditions and effectively controls competing side reactions, resulting in high yields and good functional group tolerance.
Article
Chemistry, Organic
Peter G. N. Neate, Bufan Zhang, Jessica Conforti, William W. Brennessel, Michael L. Neidig
Summary: Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, allowing for diverse coupling reactions without significant modification of the catalytic protocol. This represents a rare example of a single iron-catalyzed system effective across various coupling reactions while remaining operationally simple.
Article
Chemistry, Organic
Ikuya Fujii, Kazuhiko Semba, Yoshiaki Nakao
Summary: Rhodium-aluminum bimetallic complexes catalyze the Kumada-Tamao-Corriu (KTC) cross-coupling reaction using arylmagnesium compounds generated from corresponding aryl fluorides or chlorides. This method allows the challenging KTC coupling reaction to be carried out using aryl fluorides as nucleophiles, resulting in various biaryls.
Article
Chemistry, Organic
Quan Lin, Hegui Gong, Fan Wu
Summary: Here, we present a nickel-catalyzed reductive coupling reaction of bromopyridines with tertiary alkyl bromides, enabling the synthesis of alkylated pyridines bearing an all-carbon quaternary center. This strategy offers mild conditions, a broad substrate scope, and high functional group tolerance. We believe this method provides an alternative solution to the challenging task of synthesizing sterically congested alkylpyridines, benefiting the synthetic community and pharmaceutical industry.
Article
Chemistry, Organic
Peng Chen, Zhi-Yong Wang, Xiao-Shui Peng, Henry N. C. Wong
Summary: An efficient synthetic protocol involving iron-catalyzed cross-coupling of organolithium compounds with vinyl halides as key coupling partners is presented. Over 30 examples were obtained with moderate to good yields and high stereo-selectivities. The practicality of this method is evidenced by a gramscale synthesis, and a preliminary mechanistic investigation was also performed.
Article
Chemistry, Multidisciplinary
Daniels Posevins, Aitor Bermejo-Lopez, Jan-E. Backvall
Summary: An iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents was disclosed, allowing for efficient chirality transfer and preparation of various fluoroalkyl allenes. Additionally, an iron-catalyzed cross-coupling of Grignard reagents with alpha-alkynyl oxetanes and tetrahydrofurans was demonstrated as a straightforward approach towards fully substituted beta- or gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Eiji Shirakawa, Yuki Ota, Kyohei Yonekura, Keisho Okura, Sahiro Mizusawa, Sujan Kumar Sarkar, Manabu Abe
Summary: An electron has been found to catalyze the cross-coupling reaction of organometallic compounds with aryl halides, which is more desirable for green and sustainable chemistry compared to transition metal catalysis. However, high temperature is required for this electron catalysis. We discovered that visible light photoirradiation can accelerate the electron-catalyzed reaction by using photoredox catalysis, enabling the reaction to proceed at room temperature. The supply of the electron catalyst through photoredox catalysis also expands the scope of aryl halides.
Article
Chemistry, Multidisciplinary
Nikki J. Bakas, Pablo Chourreu, Eric Gayon, Guillaume Lefevre, Michael L. Neidig
Summary: The molecular-level role of alkoxide salts as alternative additives in iron-catalyzed cross-coupling reactions is investigated. Spectroscopic studies reveal that alkoxides promote the formation of homoleptic organoferrates, providing a non-toxic alternative to N-methylpyrrolidone for accessing reactive intermediates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Xu Luo, Dali Yang, Xiaoqian He, Shengchun Wang, Dongchao Zhang, Jiaxin Xu, Chih-Wen Pao, Jeng-Lung Chen, Jyh-Fu Lee, Hengjiang Cong, Yu Lan, Hesham Alhumade, Janine Cossy, Ruopeng Bai, Yi-Hung Chen, Hong Yi, Aiwen Lei
Summary: The authors report an on-cycle mechanism for CoCl2bpy2 catalyzed Negishi-type cross-coupling, elucidating the full catalytic cycle through multiple spectroscopic studies. Solvent and ligand were found to be crucial for generating catalytically active Co(I) species, with acetonitrile and bipyridine ligand resisting Co(I) disproportionation events. Combined investigations using Q-XAFS, EPR, IR, and DFT calculations provide comprehensive mechanistic insights into the structural information of the catalytic cobalt species and the entire Co(I)/Co(III) cycle. Additionally, the acetonitrile and bipyridine system can be extended to acylation, allylation, and benzylation reactions of aryl zinc reagents, demonstrating a broad substrate scope with a catalytic amount of Co salt. Overall, this work offers a fundamental mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions.
NATURE COMMUNICATIONS
(2023)
