Article
Chemistry, Multidisciplinary
Jing-Hong Guo, Yu Liu, Xin-Cheng Lin, Tian-Mu Tang, Bi-Qin Wang, Ping Hu, Ke-Qing Zhao, Feijie Song, Zhang-Jie Shi
Summary: In this study, an unprecedented highly selective cleavage of C1-C8 bond with the insertion of alkynes was achieved by using a blocking strategy via Ni catalysis. This provides an efficient method for the synthesis of 1,8-disubstituted naphthalenes, with the potential for easy removal of the blocking group after the transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jinyu Zhang, Deng Pan, Hao-Xiang Zhang, Nuo Yan, Xiao-Song Xue, Dongbing Zhao
Summary: The formal cross-dimerization of benzocyclobutenones (BCBs) and silacyclobutanes (SCBs) was achieved by a nickel/magnesium synergistic catalytic system, leading to the formation of eight-membered benzosilacycles. The reversal of site-selectivity in this reaction was attributed to the steric hindrance and the proper choice of catalyst.
Article
Chemistry, Organic
Manuel Barday, Eva Nicolas, Bradley Higginson, Francois Delmotte, Martin Appelmans, Christophe Aissa
Summary: This study demonstrates that a nickel catalyst can facilitate the tandem reaction of terminal alkynes with other molecules without the need for slow or sequential addition of reagents and catalysts. This approach presents a significant departure from previous reaction pathways.
SYNTHESIS-STUTTGART
(2022)
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
Shusuke Ochi, Zining Zhang, Ying Xia, Guangbin Dong
Summary: In this study, a unique one-carbon ring-expansion strategy was developed to synthesize multi-substituted 2-indanones from benzocyclobutenones and styrene-type olefins. The use of a cationic ligandless rhodium catalyst enabled high reactivity and selectivity towards the (4+1) product. The method exhibited broad functional group tolerance and scalability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Feng-Ping Zhang, Rong-Hua Wang, Jiang-Fei Li, Hao Chen, Madala Hari Babu, Mengchun Ye
Summary: In this study, an intermolecular carbophosphination reaction of alkynes with 5-membered phosphole oxides was successfully realized using a Ni-Al bimetallic catalyst, leading to the formation of a series of 7-membered phosphepines in high yields up to 94%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Mo Chen, John Montgomery
Summary: Regio- and enantioselective functionalization of heteroarene C-H bonds in the absence of directing groups has been a long-standing challenge. In this study, we developed a new approach for intermolecular enantioselective C-H alkylation of heteroarenes using nickel catalysts. The reaction can be carried out under mild conditions without the need for Lewis acid co-catalysts. Synthesis of NHC nickel complexes stabilized with 1,5-hexadiene improved the functional group tolerance and heteroarene scope. Mechanistic investigations revealed a ligand-to-ligand hydrogen transfer pathway.
Article
Chemistry, Multidisciplinary
Songjie Yu, Yinan Ai, Lingfei Hu, Gang Lu, Chunying Duan, Yue Ma
Summary: A palladium-catalyzed chemoselective coupling of readily available bicyclo[1.1.1]pentanyl alcohols (BCP-OH) with various halides has been developed, providing expedient access to a wide range of cyclobutanone and beta,gamma-enone skeletons through single or double C-C activation. The reaction exhibits broad substrate scope with both BCP-OH and halides, including natural product derivatives. Moreover, the dependence of reaction chemodivergence on base additive has been investigated, which is expected to enhance the reaction modes and synthetic potential of BCP-OH for preparing more complex molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Adam Cook, Haydn MacLean, Piers St Onge, Stephen G. Newman
Summary: A catalytic method for direct deoxygenation of various C-O bond-containing functional groups is reported. The reaction, using a Ni(II) pre-catalyst and silane reducing agent, selectively reduces alcohols, epoxides, ethers, aldehydes, and ketones to their corresponding alkanes while leaving other functional groups untouched. Practical applications in catalytic deuteration, benzyl ether deprotection, and valorization of biomass-derived feedstocks demonstrate the versatility of this methodology.
Article
Chemistry, Multidisciplinary
Ruirui Li, Xiaonan Shi, Dongbing Zhao
Summary: The utilization of cyclobutanones as synthetic precursors in transition metal catalysis has achieved great success due to their capability of cleaving the C(carbonyl)-C bond through strain release. However, most literature focuses on Rh or Ni catalysts, and the reaction involving C-H bond is still not well-developed. In this study, the authors have successfully demonstrated the first palladium-catalyzed skeletal reorganization of cyclobutanones, which involves the cleavage of both C(carbonyl)-C bonds and C-H bonds, providing a rapid approach to diverse indanones. Compared to the previous Rh-catalytic system, the Pd-catalytic system presented in this study offers distinct advantages, including the absence of a directing group to facilitate the C(carbonyl)-C bond cleavage, milder reaction conditions, and simplified work-up procedures.
CHINESE JOURNAL OF CHEMISTRY
(2023)
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)
Review
Chemistry, Applied
Oleg Y. Lyakin, Dmitry S. Bushmin, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: This review summarizes the recent advances in homogeneous oxidation of hydrocarbon C(sp(3))-H bonds catalyzed by nickel and palladium complexes, and discusses the correlations between the catalyst structure, ligand properties, catalytic conditions, and catalytic reactivity (efficiency, chemoselectivity, and regioselectivity).
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Abdoul G. Diallo, Deborah Paris, Djiby Faye, Sylvain Gaillard, Mark Lautens, Jean-Luc Renaud
Summary: This study reports a general approach for the allylation of oxa- and azabenzonorbornadienes by merging organophotoredox and nickel catalysis. The method allows for selective allylation of various heterocyclic alkene derivatives with a broader range of allylic acetate compounds. Notably, the reaction does not require air-sensitive organometallic species or metal reductants.
Article
Chemistry, Multidisciplinary
Gilles De Smet, Xingfeng Bai, Carl Mensch, Sergey Sergeyev, Gwilherm Evano, Bert U. W. Maes
Summary: This study demonstrates that acetate can serve as a renewable leaving group for selective deoxygenation of phenolics. The Ni-catalyzed reaction in a green solvent allows for efficient deoxygenation without affecting specific functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yun-Cheng Luo, Ming-Kuan Wang, Ling-Chao Yu, Xingang Zhang
Summary: Here, we report a nickel-catalyzed selective C(sp(2))-F bond alkylation of HFO-1234yf with alkylzinc reagents, resulting in 2-trifluoromethylalkenes that can serve as versatile synthons for diversified transformations. Mechanistic studies reveal that the addition of lithium salt is crucial for promoting the oxidative addition of Ni-0(L-n) to the C-F bond, and less electron-rich N-based ligands exhibit comparable or higher oxidative addition rates compared to electron-rich phosphine ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Xin-Yang Lv, Roman Abrams, Ruben Martin
Summary: The authors in this paper developed a dual catalytic strategy using ketone derivatives as one-electron handles to forge C(sp(3)) architectures through alpha C-C cleavage with aryl and alkyl bromides. This method combines the flexibility of nickel catalysis with the generation of open-shell reaction intermediates through photoredox events, offering a wide scope and broad application profile for the synthesis of functional molecules.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Mikkel B. Buendia, Bradley Higginson, Soren Kegnaes, Soren Kramer, Ruben Martin
Summary: This article describes a light-induced redox-neutral Ni-catalyzed method for sp3C-H alkylation of unactivated alkenes with alkyl bromides possessing beta-hydrogens. The method stands out for its simplicity, wide applicability, and exquisite regio- and chemoselectivity, providing an entry point to forge sp3-sp3 architectures.
Article
Chemistry, Multidisciplinary
Ciro Romano, Laura Talavera, Enrique Gomez-Bengoa, Ruben Martin
Summary: This study reports a dual catalytic manifold that allows for site-selective functionalization of unactivated sp(3) C-O bonds in cyclic acetals with aryl and alkyl halides. The reaction is initiated by an appropriate sigma*-p orbital overlap prior to sp(3) C-O cleavage, highlighting the significance of conformational flexibility in both reactivity and site selectivity. The protocol demonstrates excellent chemoselectivity, opening up new possibilities for activating strong sigma sp(3) C-O linkages.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Correction
Chemistry, Multidisciplinary
Ciro Romano, Laura Talavera, Enrique Gomez-Bengoa, Ruben Martin
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Craig S. Day, Cuong Dat Do, Carlota Odena, Jordi Benet-Buchholz, Liang Xu, Cina Foroutan-Nejad, Kathrin H. Hopmann, Ruben Martin
Summary: In this study, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes act as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is demonstrated by accessing low-valent (bipy)2Ni(0) species that are otherwise challenging to access.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Fei Cong, Riccardo S. Mega, Jinhong Chen, Craig S. Day, Ruben Martin
Summary: In this study, we report a visible-light-mediated trifluoromethylation reaction of carbonyl-type compounds and unactivated olefins using copper as a catalyst. This reaction allows for the synthesis of valuable C(sp(3))-CF3 structures from easily accessible precursors under mild conditions, making it a complementary approach for late-stage functionalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xin-Yang Lv, Roman Abrams, Ruben Martin
Summary: This article describes the development of a copper-catalyzed C(sp(3))-amination of proaromatic dihydroquinazolinones derived from ketones. The reaction utilizes open-shell species generated through homolytic C-C bond cleavage driven by aromatization. The protocol is characterized by its simplicity and generality, allowing for chemical diversification of advanced intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Franz-Lucas Haut, Riccardo S. Mega, Joan V. Estornell, Ruben Martin
Summary: We describe a catalytic intramolecular decarboxylative/desulfonylative sp(3) allylation triggered by sulfinate salts under light irradiation. The reaction likely proceeds through a non-classical, radical-polar crossover mechanism, providing a rapid and reliable method to access valuable allyl architectures from readily available precursors. The protocol is characterized by its simplicity, scalability, and the use of abundant, commercially available catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jesus Rodrigalvarez, Hao Wang, Ruben Martin
Summary: In this study, an interrupted deaminative Ni-catalyzed chain-walking strategy is disclosed, which can forge sp3-sp3 architectures at remote, yet previously unfunctionalized, methylene sp3 C-H sites enabled by the presence of native amides. This protocol is characterized by mild conditions and a wide scope, including challenging substrate combinations. Site-selectivity can be controlled by the choice of ligands, offering an opportunity to enable sp3-sp3 bond formations that are otherwise inaccessible in conventional chain-walking events.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xin-Yang Lv, Ruben Martin
Summary: Here, the development of a copper-catalyzed C-(sp(3)) amination of unactivated secondary alkyl iodides mediated by diaryliodonium salts is described. The method involves the intermediacy of aryl radical species that undergo halogen atom transfer prior to interfacing with copper catalysts, enabling the formation of C-N bonds at sp(3)-hybridized carbons. The protocol is characterized by its mild reaction conditions, excellent regioselectivity, and wide substrate scope.
Article
Chemistry, Physical
Laura Talavera, Robert R. A. Freund, Huihui Zhang, Matthew Wakeling, Mara Jensen, Ruben Martin
Summary: In this study, a novel Ni-catalyzed 1,1-difunctionalization reaction of unactivated terminal alkenes is disclosed, allowing for the incorporation of two different heteroatom motifs across an olefin backbone. This method provides a streamlined approach to the synthesis of alpha-aminoboronic acid derivatives from simple precursors and exhibits simplicity and generality across a wide range of coupling counterparts.
Article
Chemistry, Physical
Craig S. S. Day, Angel Renteria-Gomez, Stephanie J. J. Ton, Achyut Ranjan Gogoi, Osvaldo Gutierrez, Ruben Martin
Summary: Polypyridine-ligated nickel complexes are widely used as privileged catalysts in cross-coupling reactions due to their ability to shuttle between different oxidation states. However, the mechanistic understanding of these reactions is limited. In this study, the reactivity of pseudohalide- and halide-ligated Ni(II) complexes with polypyridine ligands in electron-transfer reactions is investigated. Electrochemical techniques and quantum mechanical calculations support the observations regarding the different behaviors of Ni(II) halide and pseudohalide complexes. Reactivation of catalytically inactive Ni(II) pseudohalide complexes in the presence of exogenous salts is also demonstrated. Overall, this study provides insights into the overlooked steps in Ni-catalyzed cross-coupling reactions and offers guidance for future reaction design.
Article
Chemistry, Multidisciplinary
Wen-Jun Yue, Ruben Martin
Summary: This paper describes a method for α-difluoroalkylation of benzyl amines with trifluoromethylarenes. The protocol is characterized by its simplicity, excellent selectivity, and broad applicability, even with advanced synthetic intermediates, providing a new entry point for the preparation of medicinally-relevant α-difluoroalkylated amines from simple, accessible precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Laura Talavera, Robert R. A. Freund, Huihui Zhang, Matthew Wakeling, Mara Jensen, Ruben Martin
Summary: Here, a novel Ni-catalyzed 1,1-difunctionalization of unactivated terminal alkenes is disclosed, allowing for the incorporation of two different heteroatom motifs across an olefin backbone. This streamlines the access to alpha-aminoboronic acid derivatives from simple precursors, and the method exhibits simplicity and generality across a wide range of coupling counterparts.
Review
Chemistry, Multidisciplinary
Craig S. Day, Ruben Martin
Summary: This review discusses the importance of disproportionation and comproportionation reactions in organometallic chemistry and catalysis, as well as their impact on the stability of metal complexes. Furthermore, it analyzes the factors contributing to these reactions and their role in Ni- and Cu-catalyzed transformations.
CHEMICAL SOCIETY REVIEWS
(2023)
