Article
Chemistry, Multidisciplinary
Cole L. Cruz, John Montgomery
Summary: A mild and convenient coupling reaction between aliphatic aldehydes and unactivated alkyl bromides has been developed using a common Ni(II) precatalyst and a readily available bioxazoline ligand, affording silyl-protected secondary alcohols. The reaction is operationally simple, utilizes Mn as a stoichiometric reductant, and tolerates a wide range of functional groups. The presence of 1,5-hexadiene as an additive plays a crucial role in optimizing yields.
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
Multidisciplinary Sciences
Jinwei Sun, Yongze Zhou, Rui Gu, Xin Li, Ao Liu, Xuan Zhang
Summary: Here, the authors report a nickel-catalyzed method for the silylative alkylation of activated olefins using chlorosilanes and alkyl bromides. This approach enables the efficient synthesis of alkylsilanes with diverse structures and demonstrates good functional group tolerance. The method can also be applied for the functionalization of bioactive molecules.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Abing Duan, Yali Yu, Fengqin Wang, Xueqiang Wang, Dongbo Wang
Summary: Density functional theory calculations were performed to study the reaction mechanism of bromoalkynes, revealing that the electrostatic effect caused by different charge distributions of reactants is the main reason for the preference of Ni(I) species for alkyne syn-insertion over Ni(II) species. The radical pathway exhibits a lower energy barrier, indicating its advantage in terms of kinetics. The product configuration is determined by both distortion energy and steric hindrance.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Peng Wang, Yaxin Wang, Helfried Neumann, Matthias Beller
Summary: A general rhodium-catalyzed selective carbonylative coupling method is presented for the first time, where unactivated alkyl chlorides are coupled with aliphatic alcohols or phenols to form esters. The addition of sodium iodide plays a crucial role in providing more active alkyl iodides in situ. The Rh(i)-DPPP catalyst system enables the preparation of diverse esters, including industrially relevant acetates, in high yields.
Article
Multidisciplinary Sciences
Geun Seok Lee, Daeun Kim, Soon Hyeok Hong
Summary: The use of alkyl chlorides in Pd-catalyzed Mizoroki-Heck coupling reactions remains a challenging issue due to the high thermodynamic barrier of alkyl chloride activation and the propensity of alkylpalladium complexes to undergo undesired beta-hydride elimination. However, this study demonstrates that alkyl chlorides, including tertiary ones, can efficiently participate in Mizoroki-Heck cross-coupling reactions under mild conditions via photoinduced Pd catalysis, offering great potential for late-stage functionalizations and molecular complexity.
NATURE COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Pengfei Li, Chengcheng Guo, Siyi Wang, Dengke Ma, Tian Feng, Yanwei Wang, Youai Qiu
Summary: We reported a facile and general method for electroreductive deuteration of unactivated alkyl halides or pseudo-halides using D2O as the deuterium source. This method works well for various alkyl halides, including sterically hindered tertiary chlorides, and achieves high deuterium incorporation in organic synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Qi Wang, Zhong-Lin Zang, Mi Jie, Li-Hua Luo, Dan Yang, Cheng-He Zhou, Gui-Xin Cai
Summary: The Cu-catalyzed high-chemoselective trifluoromethylation reactions of unactivated cycloalkenes have been explored through the modulation of appropriate ligands. The Cu(I)/appropriate ligands-catalytic systems provide a ligand-controlled approach for site-specific spiro-aryltrifluoromethylation and chlorotrifluoromethylation. Additionally, 1,2-dichloroethane is used as a greener and more economical feedstock for chlorotrifluoromethylation compared to other chlorine sources.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Physical
Shidheshwar B. Ankade, Anand B. Shabade, Vineeta Soni, Benudhar Punji
Summary: This review summarizes the transition-metal-catalyzed alkylations of C-H bonds on various arenes and heteroarenes using unactivated alkyl halides until October 2020. The review is divided into two major sections based on the substrates utilized for alkylation: alkylation of arenes and alkylation of heteroarenes. Substantial progress has been made in direct alkylation using primary, secondary, and tertiary alkyl halides as well as methylation and fluoroalkylation.
Article
Chemistry, Organic
Ning Cui, Tingzhi Lin, Yan-En Wang, Jian Wu, Yuheng Han, Xinyang Xu, Fei Xue, Dan Xiong, Patrick J. Walsh, Jianyou Mao
Summary: A nickel-catalyzed reductive cross-coupling reaction has been developed for the synthesis of aryl alkyl ketones from aryl cyclopropyl ketones and unactivated alkyl bromides. The reaction proceeds via radical cleavage of the alkyl bromide, and provides access to a variety of gamma-alkyl-substituted ketones through ring opening of cyclopropyl ketones (26 examples, 50-90% yield).
Article
Chemistry, Organic
Xingjie Zhang, Di Qi, Chenchen Jiao, Zhiguo Zhang, Xiaopan Liu, Guisheng Zhang
Summary: The direct iminoalkynylation of unactivated olefins with terminal alkynes was achieved for the first time using nickel-catalyzed cascade reaction, enabling the construction of challenging C(sp(3))-N and C(sp(3))-C(sp) bonds in a single step for the synthesis of a variety of N-heterocycles. The method shows good potential for widespread applications in synthetic chemistry, biochemistry, and materials science.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Ming Li, Yuke Li, Wan-Yuan Jia, Guo-Qing Sun, Fan Gao, Guo-Xiao Zhao, Yi-Feng Qiu, Xi-Cun Wang, Yong-Min Liang, Zheng-Jun Quan
Summary: The free radical cyclization reaction is a promising strategy for the formation of ring frameworks. In this study, we report a copper-catalyzed tandem radical cyclization strategy for preparing substituted lactam derivatives. This reaction utilizes a radical coupling approach, allowing a wide range of alkenes and being compatible with primary, secondary, and tertiary radicals. Density functional theory calculations were also performed to gain insights into the reaction mechanism.
Article
Multidisciplinary Sciences
Guo-Quan Sun, Wei Zhang, Li-Li Liao, Li Li, Zi-Hao Nie, Jin-Gui Wu, Zhen Zhang, Da-Gang Yu
Summary: In this study, the authors successfully transformed unactivated aryl and alkyl (pseudo)halides into carboxylic acids using nickel catalysis and electricity, with atmospheric CO2 as the carbon source. This sustainable and economic strategy features mild conditions, inexpensive catalyst, and a broad substrate scope, avoiding the use of sacrificial electrodes. The reaction mechanism involves oxidative addition of aryl halides to Ni(0) complex, reduction of aryl-Ni(II) adduct to Ni(I) species, and carboxylation with CO2.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Fei Wang, Weidong Rao, Shun-Yi Wang
Summary: A practical and scalable method for the synthesis of unsymmetrical sulfides through cross-electrophile coupling between unactivated alkyl bromides and arenesulfonyl cyanides catalyzed by Ni(acac)(2) under reductive conditions has been developed. This catalytic strategy offers a complementary approach for the preparation of unsymmetrical alkyl-aryl sulfides with good functional group tolerance under mild conditions. It relies on readily available, unfunctionalized materials such as alkyl (pseudo)halides.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Riccardo Giovanelli, Lorenzo Lombardi, Riccardo Pedrazzani, Magda Monari, Marta Castineira Reis, Carlos Silva Lopez, Giulio Bertuzzi, Marco Bandini
Summary: A carbonylation-carboxylation synthetic sequence is achieved via double CO2 fixation. The combination of Ni-catalyzed cross-electrophile coupling and AlCl3 triggers a cascade reaction resulting in the formation of three consecutive C-C bonds in a single operation. This strategy provides a novel synthesis route for ketones through Lewis acid-assisted carbon dioxide valorization, demonstrated by computational insights and labeling experiments.
Article
Chemistry, Organic
Shitang Xu, Rongnan Yi, Chunling Zeng, Yue Cui, Xue-Qiang Wang, Xinhua Xu, Ningbo Li
Summary: Various indole-containing compounds have shown impressive pharmaceutical activities, but their functionalization usually relies on organic solvents, which is not environmentally friendly. To address this, researchers developed regiospecific sulfenylation, selenylation, and telluration of indoles using H2O as solvent. This protocol offers simple operation, mild conditions, wide substrate scope, excellent functional group tolerance, and recyclability, allowing for convenient synthesis of 3-chalcogenyl-indoles.
Article
Multidisciplinary Sciences
Xiao-Jing Zhang, Zhuo Zhao, Xia Wang, Min-Hui Su, Lili Ai, Yingying Li, Quan Yuan, Xue-Qiang Wang, Weihong Tan
Summary: A new chemical tailoring strategy was developed to efficiently produce circular bivalent aptamers and cyclized DNA sequences. These modified molecules exhibited high nuclease resistance and significantly improved binding, targeting, and tumor tissue enrichment abilities, thus showing great potential for biomedical applications.
NATIONAL SCIENCE REVIEW
(2023)
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
Bo-Wei Zhao, Liu Yang, Cheng-Yu Long, Han-Lu Li, Yu-Ting He, Xue-Qiang Wang
Summary: In this study, a Ni-catalyzed coupling strategy for the synthesis of diphenic acid derivatives was developed, and these acids were then used in the synthesis of Pt(II) agents.
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, Multidisciplinary
Guo-Rong Zhang, Weihong Tan, Xue-Qiang Wang
Summary: This study presents a subzero-temperature-enabled molecule stacking strategy for the on-demand tailoring of aptamer glues for the precision recognition and efficient degradation of membrane protein. The strategy significantly enhances the specific recognition ability and binding affinity of aptamer glues, allowing the distinction of targeted cell lines. Additionally, the engineered aptamer glue demonstrates impressive targeted cell membrane protein degradation ability, which holds great potential for advancing cancer diagnosis and targeted therapy.
Article
Chemistry, Analytical
Shen-Huan Li, Guo-Rong Zhang, Yu-Ting He, Liu Yang, Han-Lu Li, Cheng-Yu Long, Yue Cui, Xue-Qiang Wang
Summary: This study introduces novel chemiluminescent probes with tunable emission wavelengths, which can detect various analytes with high specificity. These probes have been successfully applied in bioimaging of cancer cells and macrophage cells.
ANALYTICAL CHEMISTRY
(2023)
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)
Correction
Chemistry, Organic
Bo-Wei Zhao, Liu Yang, Cheng-Yu Long, Han-Lu Li, Yu-Ting He, Xue-Qiang Wang
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)
