Article
Chemistry, Multidisciplinary
Lingpu Meng, Jingjie Yang, Mei Duan, You Wang, Shaolin Zhu
Summary: Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed using NiH catalysis with a simple bioxazoline ligand under mild conditions. A variety of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by employing nitroarenes, hydroxylamines and dioxazolones as amination reagents. Chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lu Wang, Minxu Shi, Xiaoping Chen, Nicholas Su, Weili Luo, Xiaheng Zhang
Summary: In this study, aromatic N-heterocyclic radicals were generated and utilized for the functionalization of unactivated alkenes, leading to the efficient synthesis of alkylated N-heterocyclic amines with medicinal relevance. This approach offers a novel retrosynthetic disconnection for the synthesis of therapeutic molecules and can be extended to the synthesis of densely functionalized heterocyclic amines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Efrey A. Noten, Rory C. McAtee, Corey R. J. Stephenson
Summary: This research discloses an intramolecular reaction that utilizes a nitrogen radical to form a C-N bond and repurposes the nitrogen atom's activating group to form a C-C bond, enabling the efficient synthesis of arylethylamines. The protocol utilizes photoredox catalysis under mild conditions.
Article
Chemistry, Organic
Gautam Kumar, Zheng-Wang Qu, Stefan Grimme, Indranil Chatterjee
Summary: Catalytic hydroarylation reactions of conjugated dienes using tris(pentafluorophenyl)borane as a Lewis acid catalyst show a broad substrate scope for highly regioselective functionalization of sterically hindered aniline derivatives. Experimental and theoretical studies reveal the crucial role of residual water and B(C6F5)(3) complex in the reaction mechanism.
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
Chemistry, Organic
Sayan K. Jana, Mamata Maiti, Purusattam Dey, Biplab Maji
Summary: A facile synthesis method for mono-, 1,1-and 1,2-disubstituted cyclopropanes via visible light-mediated photoredox/nickel dual catalysis under mild conditions was demonstrated. Mechanistic inspection and control experiments revealed the importance of dual catalysis and the reaction proceeds via a stepwise oxidative addition followed by an intramolecular S(N)2 reaction.
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
Chemistry, Physical
Yiting Hao, Xinlin Wang, Yumeng Wu, Liangliang Song, Kui Zhang, Lingchao Cai
Summary: A concise and modular method for the synthesis of chiral organic compounds bearing pyridyl-substituted stereogenic centers has been established. The method enables the introduction of stereogenic C-(sp(3)) centers into widely available alkenes via a nickel/Box catalyst with alpha-pyridyl alkyl bromide. The reaction conditions are mild and allow for a wide substrate scope and good functional-group tolerance, resulting in the formation of various enantioenriched alkylated pyridine derivatives with high yields and enantioselectivities. Further application of enantioenriched pyridine derivatives is demonstrated through an asymmetric Si-H bond insertion reaction, showcasing the productive utility of this modular strategy.
Article
Chemistry, Physical
Dandan Yang, Hai Huang, He Zhang, Li-Ming Yin, Mao-Ping Song, Jun-Long Niu
Summary: The study achieved the Co-H-catalyzed intermolecular hydroamination of unactivated alkenes with various amine electrophiles by introducing a removable directing group. The catalytic system showed substrate-dependent regioselectivity, broad substrate scope, and simplified reaction conditions, providing a general and flexible protocol for the preparation of various amino acid derivatives.
Article
Chemistry, Physical
Peng-Fei Yang, Jian-Xing Liang, Han -Tong Zhao, Wei Shu
Summary: In this study, a straightforward method to access enantioenriched 1,n-diamines containing a chiral alpha-branched aliphatic amine is achieved through Ni-catalyzed asymmetric hydroamination. This method delivers good yields and excellent enantioselectivities with diverse substitution patterns, and exhibits excellent functional group tolerance.
Article
Chemistry, Multidisciplinary
Peng-Wei Sun, Ze Zhang, Xinyao Wang, Linshan Li, Yuxin Li, Zhengming Li
Summary: Metal-catalyzed hydroamination of alkenes is an effective method for synthesizing amines. This study developed a cobalt-catalyzed intermolecular hydroamination reaction using NFSI as the nitrogen source, which exhibited excellent selectivity and yield.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhu Cao, Huihui Zhang, Xinxin Wu, Yahong Li, Chen Zhu
Summary: The research achieved the heteroarylation of unactivated aliphatic C-H bonds through radical-mediated heteroaryl migration, leading to a variety of heteroaryl-substituted aliphatic ketones. The method is applicable to O-/S-/N-containing heteroaryls and features mild C-C bond cleavage and good selectivity for tertiary C-H bonds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Xiang Lyu, Changhyeon Seo, Hoimin Jung, Teresa Faber, Dongwook Kim, Sangwon Seo, Sukbok Chang
Summary: Synthetic methods for constructing enantioenriched beta-lactams are highly valuable and challenging due to the formation of strained four-membered rings. This study presents a NiH-catalysed strategy using alkenyl dioxazolone derivatives to overcome the regioselectivity issue. The reaction demonstrates excellent regioselectivity regardless of the electronic properties of substituents and offers a convenient access to enantioenriched beta-lactams.
Article
Chemistry, Organic
Avishek Kumar Jha, Dhananjay P. Nair, Munaifa Arif, Girish Suresh Yedase, Rositha Kuniyil, Veera Reddy Yatham
Summary: In this study, a metal-free and redox-neutral radical reaction strategy was reported. Utilizing an organo photocatalyst, N-arylacrylamides reacted with unactivated alkyl chlorides to undergo radical cascade addition and cyclization, giving moderate to good yields of 3,3-disubstituted oxindoles. The method showed mild reaction conditions and wide substrate scope, and also allowed the utilization of aryl chlorides for the radical cyclization reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akshi Tyagi, Sunita Mondal, Anmol, Vikas Tiwari, Tarak Karmakar, Subrata Kundu
Summary: The research demonstrates that the hydroamination of electron-deficient olefins can be efficiently carried out using the (CAAC)Cu-Cl catalyst at room temperature and under an open atmosphere, and the catalyst also shows excellent efficiency in the hydroaryloxylation and hydroalkoxylation of alkenes. Detailed computational studies reveal that the reaction proceeds via either a four-membered or a six-membered cyclic transition state containing the copper ion.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ryan T. McGuire, Arun A. Yadav, Mark Stradiotto
Summary: The report presents the first Ni-catalyzed N-arylation of beta-fluoroalkylamines with broad scope. The use of a stable pre-catalyst allows for reactions to be conducted at room temperature or using a commercially available dual-base system, providing a mild protocol with broad substrate scope and enantioselective transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Travis Lundrigan, Joseph P. Tassone, Mark Stradiotto
Summary: In this study, a novel approach for the nickel-catalyzed N-arylation of amides using an organic amine base as a catalyst was successfully demonstrated. By employing a specific catalyst mixture and dual-base system, a diverse range of electrophiles were cross-coupled with structurally diverse nucleophiles.
Article
Chemistry, Physical
Takahiko Ogawa, Fabien Lindeperg, Mark Stradiotto, Laura Turculet, Orson L. Sydora
Summary: Steric reduction principles were applied in PN ligand design to improve 1-octene selectivity in chromium catalysis. Novel phosphole and phospholane-based PN ligands were prepared and compared with benchmark systems, showing higher overall product selectivity. The relationship between 1-octene selectivity and ligand bite angle was explored, revealing the need for more sophisticated modeling to account for differences in selectivity.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Nicholas E. Bode, Joseph P. Tassone, Michael J. Ferguson, Mark Stradiotto
Summary: The synthesis and characterization of new complexes (CyPBn-Cy)NiCl2 and (CyPBn-Cy)Ni(o-tol)Cl were reported, and a comparison of their catalytic behavior with precatalyst complexes (L)Ni(o-tol)Cl showed that CyPBn-Cy can be competitive and complementary to the well-established JosiPhos ligand CyPF-Cy in Ni-catalyzed cross-couplings.
Article
Chemistry, Physical
Kathleen M. Morrison, Ryan T. McGuire, Michael J. Ferguson, Mark Stradiotto
Summary: This study reveals a new Ni-catalyst with unique ability to promote the cross-coupling of tertiary aliphatic alcohols with (hetero)aryl halides or phenol derivatives. Exploration of substrate scope and competition experiments shed light on the capabilities and reactivity preferences of this catalyst system.
Article
Chemistry, Multidisciplinary
Ryan T. McGuire, Travis Lundrigan, Joshua W. M. MacMillan, Katherine N. Robertson, Arun A. Yadav, Mark Stradiotto
Summary: This article introduces a new efficient protocol for the C-N cross-coupling of amides and (pseudo)halide-substituted acetophenones. The reaction can be conducted at room temperature and employs nickel catalysts and organic amine bases. Stoichiometric experiments support a Ni-0/II pathway, and the combination of DBU/NaTFA enables room-temperature amide cross-couplings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Connor M. Simon, Samantha L. Dudra, Ryan T. McGuire, Michael J. Ferguson, Erin R. Johnson, Mark Stradiotto
Summary: This study reveals a new reductive elimination pathway for nickel-catalyzed C-N cross-coupling, involving a bifurcated pathway and a base-promoted pathway for C-N reductive elimination.
Article
Chemistry, Organic
Joseph P. Tassone, Travis Lundrigan, Trent D. Ashton, Mark Stradiotto
Summary: This study successfully synthesized potentially useful 4-amino-1,8-naphthalimides fluorescent probes using a new method, highlighting the significance of Ni-catalyzed reactions in this process.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Travis Lundrigan, Joseph P. Tassone, Mark Stradiotto
Summary: A novel and efficient method for the C-N cross-coupling of (hetero)aryl (pseudo)halides with optically pure alpha-amino acid esters using a commercially available nickel catalyst and weak inorganic base was developed. This represents the first successful example of Ni-catalyzed N-arylation of amino acid esters without employing electrochemistry, allowing for high yields and excellent enantioselectivity in the coupling reaction between a variety of amino acid tert-butyl esters and (hetero)aryl chlorides, bromides, and tosylates. The use of a bulky amino acid ester group was found to limit the extent of base-mediated racemization of the product.
CANADIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nicole Martinek, Kathleen M. M. Morrison, Justin M. M. Field, Samuel A. A. Fisher, Mark Stradiotto
Summary: This study presents a systematic evaluation of the DalPhos ligand family in nickel-catalyzed N-arylation chemistry. The evaluation involved primary and secondary alkylamines as well as a primary five-membered heteroarylamine. By combining various test electrophiles and bases, optimal ligand/catalyst identification was achieved, and limitations in the methodology were revealed. Additionally, the study led to the development of an efficient catalyst system for heteroatom-dense C-N cross-coupling.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Nicholas E. Bode, Ryan T. McGuire, Mark Stradiotto
Summary: In this study, an effective catalyst system, PhPAd-DalPhos/NiCOD2, was identified and applied for the O-arylation of substituted phenols with chloropyridine-type electrophiles under thermal conditions, leading to pyridyl-O-aryl frameworks that are present in active pharmaceutical ingredients.
Article
Chemistry, Inorganic & Nuclear
Connor M. Simon, Katherine N. Robertson, Patrick L. DeRoy, Arun A. Yadav, Erin R. Johnson, Mark Stradiotto
Summary: In this study, we report on the Ni-catalyzed C-N cross-couplings using sulfinamide nucleophiles. The results indicate that inexpensive and abundant (hetero)aryl chlorides are suitable reaction partners. Additionally, we investigate the mechanism of C-N reductive elimination through experimental and computational studies, revealing deprotonation as the preferred pathway in this reaction.
Article
Chemistry, Multidisciplinary
Kathleen M. Morrison, Charles S. Yeung, Mark Stradiotto
Summary: A systematic evaluation of competitive bisphosphine/Ni-catalyzed C-N versus C-O cross-couplings involving model compounds enabled the development of selective O- and N-arylation of amino alcohols with (hetero)aryl chloride electrophiles, without the need for protection group chemistry. The use of the CyPAd-DalPhos pre-catalyst C2 allowed for challenging O-arylation in amino alcohols with branched alkylamine groups, while selective N-arylation was observed in substrates with less hindered linear alkylamine and aniline groups. The reaction scope in (hetero)aryl chloride was broad, and the transformations could be conducted using benchtop handling of materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Michael J. Cotnam, Nicole Martinek, Mark Stradiotto
Summary: This study reveals the potential activating effect of added aluminum triflate on the catalytic C-N cross-coupling reaction of primary amides with (hetero)aryl chlorides. The use of aluminum triflate leads to dramatically improved conversion in some cases, while furfurylamine exhibits catalytic inhibition. The reaction outcome is influenced by the interplay between the DalPhos ligand and aryl group within the Ni pre-catalyst, as well as the identity of the cross-coupling partners.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Kathleen M. Morrison, Mark Stradiotto
Summary: Transition-metal catalysis has played a significant role in carbon-heteroatom bond-forming reactions. Recent advancements in Ni-catalyzed cross-couplings have shown competitive and even superior reactivity compared to Pd or Cu-based processes. Among these developments, the Ni-catalyzed C-O cross-coupling of alcohols and (hetero)aryl (pseudo)halides has emerged as an effective strategy for synthesizing (hetero)aryl ethers.
SYNTHESIS-STUTTGART
(2023)
