Article
Multidisciplinary Sciences
Bingnan Du, Chun-Ming Chan, Pui-Yiu Lee, Leong-Hung Cheung, Xin Xu, Zhenyang Lin, Wing-Yiu Yu
Summary: The authors developed diverse 2,2-difluorovinyl benzoates as versatile building blocks for modular synthesis of gem-difluoroenol ethers and gem-difluoroalkenes using nickel-catalyzed cross coupling. The method allows for late-stage functionalization of multifunctionalized bioactive molecules due to the diversity of the building blocks and excellent functional group tolerance.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
He Sheng, Qiang Liu, Bei-Bei Zhang, Zhi-Xiang Wang, Xiang-Yu Chen
Summary: This report presents a study on the blue light-induced N-heterocyclic carbene (NHC)-catalyzed single electron reduction method for the synthesis of biaryl cross-coupling products. It was found that under blue light irradiation, the NHC/tBuOK combination could construct powerful photoactive architectures to promote single electron transfer for the reduction of C-aryl-F bonds, resulting in the formation of highly reducing NHC radical anions. It was also observed that this strategy successfully reduced C-aryl-O, C-aryl-N, and C-aryl-S bonds for biaryl cross-couplings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Ye Yuan, Muliang Zhang, Xiaodong Tang, Jared L. Piper, Zhi-Hui Peng, Jun-An Ma, Jie Wu, Fa-Guang Zhang
Summary: We have developed a photoredox platform that utilizes sulfinate as a radical-relay precursor and a sacrificial nucleofuge, allowing for the construction of styrenyl polyfluoro (hetero)arenes with branch selectivity. This protocol combines photoredox catalysis, radical-radical coupling, and an elimination process in a one-pot operation, providing a mild and efficient method to access polyfluoro (hetero)aryl derivatives of natural products and drugs.
Review
Chemistry, Organic
Wengang Xu, Qiao Zhang, Qi Shao, Congjian Xia, Mingbo Wu
Summary: The recent development of photocatalytic C-F bond activation of fluorinated compounds, including fluoroarenes, gem-difluoroalkenes, and trifluoromethylarenes, has provided an efficient way to synthesize novel fluorinated products and degrade stable fluorinated pollutants. The light-induced direct C-F bond activation under mild conditions for the production of various functionalities is considered one of the most advanced and efficient methodologies in organic transformations.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Naoyuki Toriumi, Kazuya Yamashita, Nobuharu Iwasawa
Summary: In this study, a metal-free photoredox-catalyzed hydrodefluorination of fluoroarenes was achieved using N,N,N',N'-tetramethyl-para-phenylenediamine (1) as a strong photoreduction catalyst. This reaction was not only applicable to electron-rich monofluoroarenes but also to polyfluoroarenes, producing non-fluorinated arenes. Experimental mechanistic studies revealed the crucial role of the amide solvent NMP in regenerating the photocatalyst, enabling additive-free photoreduction catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Multidisciplinary Sciences
Kaluvu Balaraman, Christian Wolf
Summary: This study demonstrates the chemodivergent activation of monofluoroalkyl compounds towards either nucleophilic or electrophilic intermediates, expanding the scope of organofluorine chemistry and creating new synthetic opportunities for carbon-carbon and carbon-heteroatom bond formations.
Article
Chemistry, Physical
Jin Zhang, Jiale Liu, Xiaogang Wang, Xinkan Yang, Yangmin Ma, Ran Fang, Qun Zhao, Michal Szostak
Summary: This study reports a ruthenium-catalyzed site-selective arylation of C-F bonds in polyfluoroarenes, enabling the synthesis of complex multifluorinated biaryls. This approach exhibits broad scope and functional group tolerance, allowing for the preparation of polyfluorinated ligands, heterocycles, pharmaceuticals, and porphyrin analogues.
Article
Chemistry, Multidisciplinary
Zheng-Jia Shen, Chen Zhu, Xiao Zhang, Chao Yang, Magnus Rueping, Lin Guo, Wujiong Xia
Summary: This article describes a selective (deutero)hydrodefluorination reaction via electrolysis, which achieves remarkable chemoselectivity control by the addition of different organoboron sources. The method is operationally simple, scalable, and provides access to high-value building blocks for medicinal chemistry in one step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Elisa Y. Lai, Binbin Yuan, Lutz Ackermann, Magnus J. Johansson
Summary: In this study, a new method for directed ruthenium-catalyzed C-H aminocarbonylation has been developed under mild conditions through high-throughput experimentation. This method allows the introduction of special amide functional groups and is applicable to various substitution patterns and different weakly Lewis basic directing groups in anilides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fu-Peng Wu, Xing-Wei Gu, Hui-Qing Geng, Xiao-Feng Wu
Summary: An unprecedented and challenging defluorinative arylboration has been achieved using a copper catalyst. This method provides a flexible and facile approach to obtain a diverse range of products from polyfluoroarenes under mild reaction conditions. Furthermore, an enantioselective defluorinative arylboration was successfully realized by employing a chiral phosphine ligand, resulting in chiral products with unprecedented levels of enantioselectivity.
Article
Chemistry, Multidisciplinary
Juan Zhang, Shasha Geng, Zhang Feng
Summary: Organoboron and organosilane compounds are widely used in organic synthesis and pharmaceuticals. The functionalization of the C-F bond provides opportunities for the development of new medicinal compounds. Late-stage functionalization through defluoroborylation and defluorosilylation reactions shows promise in diversifying structures and creating new ideas for further research in this field.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Soumen Ghosh, Zheng-Wang Qu, Suman Pradhan, Avisek Ghosh, Stefan Grimme, Indranil Chatterjee
Summary: This study presents a novel visible light photoredox catalytic method for the selective cleavage of a single strong C-F bond in trifluoromethyl ketones. The reaction shows excellent chemoselectivity and functional group tolerance under mild conditions, and high-level DFT calculations are used to elucidate the mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yue Zhao, Bin Fu, Simin Wang, Yanfei Li, Xiuping Yuan, Jianjun Yin, Tao Xiong, Qian Zhang
Summary: A catalytic defluorinative boroarylation of alkenes with polyfluoroarenes and B(2)pin(2) was achieved using a PCy3-ligated copper catalyst. This method demonstrated good functional group compatibility and proceeded under mild reaction conditions, avoiding the need for stoichiometric quantities of organometallics. Valuable boronate-containing polyfluoroarenes, including challenging all-carbon quaternary carboncenter-containing triaryl alkylboronates, were efficiently synthesized.
Letter
Chemistry, Organic
Yue Zhao, Bin Fu, Simin Wang, Yanfei Li, Xiuping Yuan, Jianjun Yin, Tao Xiong, Qian Zhang
Summary: A catalytic defluorinative boroarylation of alkenes with polyfluoroarenes and B(2)pin(2) using a PCy3-ligated copper catalyst was developed. This method utilizes stable alkenes as latent nucleophiles and avoids the need for stoichiometric quantities of organometallics. It offers good functional group compatibility and operates under mild reaction conditions, enabling the efficient preparation of valuable boronate-containing polyfluoroarenes.
Article
Chemistry, Multidisciplinary
Hsuan-Hung Liao, Shao-Chi Lee, Hsin Kao, Yu-Ling Hsu, Che-Ming Hsu, Yong-Ting Tsao, Shinje Minoza, Li-Yun Li, Zong-Nan Tsai, Kuei-Chen Chang, Cheng-Ku Cheng, Cheng-Lin Chan, Yi-Sian Chien, Cheng-chau Chiu
Summary: This article presents a new method for synthesizing perfluoroaryl sulfides, which can be conducted at ambient conditions or as industrial processes, with a wide tolerance for various functional groups. The reaction mechanism involves a nucleophilic attack of a thiol group on an electron-poor aromatic ring, with a predicted stepwise or concerted mechanism.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
William J. M. Blackaby, Katie L. M. Harriman, Samuel M. Greer, Andrea Folli, Stephen Hill, Vera Krewald, Mary F. Mahon, Damien M. Murphy, Muralee Murugesu, Emma Richards, Elizaveta Suturina, Michael K. Whittlesey
Summary: A new series of homoleptic Ni(I) bis-N-heterocyclic carbene complexes with different torsion angles between the ligands have been reported. The complexes exhibit a strongly anisotropic g-tensor and the first excited state energy ranges from 270 to 650 cm(-1). The magnetic relaxation is dominated by Raman and direct processes, and the temperature dependence of the relaxation does not correlate with the torsion angle.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lia Sotorrios, Fedor M. Miloserdov, Anne-Frederique Pecharman, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey
Summary: The syntheses, reactivity, and electronic structure analyses of [Ru(PPh3)(2)(ZnMe)(4)H-2] and [Ru(PPh3)(2)(ZnPh)(4)H-2] are reported. [Ru(PPh3)(2)(ZnMe)(4)H-2] exhibits an 8-coordinate Ru center with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in [Ru(PPh3)(2)(ZnMe)(4)H-2] undergo facile, sequential exchange with ZnPh2 to give [Ru(PPh3)(2)(ZnPh)(4)H-2], which shows a 3 : 1 arrangement of ZnPh ligands. Mechanisms for ZnMe/ZnPh exchange and isomerization are proposed using DFT calculations, and the relationships of these {Ru(ZnR)(4)H-2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Claire N. Brodie, Lia Sotorrios, Timothy M. Boyd, Stuart A. Macgregor, Andrew S. Weller
Summary: The dehydropolymerization of H3B • NMeH2 to form N-methylpolyaminoborane using neutral and cationic catalysts based on the {Ir(iPr-PNHP)} fragment has been studied. The cationic catalysts showed higher activity and selectivity compared to the neutral catalysts. Density functional theory calculations revealed the mechanism of the amine-borane dehydrogenation and suggested a lower barrier for the cationic system.
Article
Chemistry, Physical
M. Arif Sajjad, Stuart A. Macgregor, Andrew S. Weller
Summary: Non-covalent interactions surrounding cationic Rh s-alkane complexes in crystal structures were analyzed using QTAIM and IGMH approaches. Both structures showed the cations residing in an octahedral array of [BAr4F](-) anions, with the [1-NBA](+) cation system exhibiting more C-HF contacts to the anions. QTAIM and IGMH analyses revealed the strongest atom-atom non-covalent interactions between the cation and anion. The IGMH approach highlighted the directionality of C-HF contacts and the significance of C-Hπ interactions.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kramer, F. Mark Chadwick, Stuart A. Macgregor, Andrew S. Weller
Summary: This study uses density functional theory calculations to model the selective exo-H/D exchange in a Rh sigma-alkane complex. The results show that exo-H/D exchange is kinetically more accessible than endo-H/D exchange, and the solid-state environment significantly affects the calculated energetics.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Connie J. Isaac, Cameron Wilson, Arron L. Burnage, Fedor M. Miloserdov, Mary F. Mahon, Stuart A. Macgregor, Michael K. Whittlesey
Summary: In this study, a novel P-Al(Me)-P pincer ligand, AlMePhos, was synthesized, and a Ru-Al heterobimetallic complex was successfully prepared. The structure was characterized by experimental and computational methods, and the reaction mechanism was investigated. Additionally, it was found that the Lewis acidity of the ligand is enhanced depending on the type of ligand.
INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Stuart A. Macgregor, Alan J. Welch
Summary: A number of (hetero)boranes are known where an atom X connects a B-B bond on the open face. In this study, an approach to distinguish between X as a bridge or a vertex in a larger cluster is described. Atom X is found to be better regarded as a vertex, with a verticity of approximately 60-65%.
Article
Chemistry, Physical
Matthew E. Grundy, Lia Sotorrios, Milan Kumar Bisai, Kang Yuan, Stuart A. Macgregor, Michael J. Ingleson
Summary: [(NacNac)Zn(DMT)][B(C6F5)4], 1, was synthesized and demonstrated as an efficient catalyst for the C-H borylation of (hetero)arenes using catecholborane. Computational studies revealed a plausible mechanism involving displacement of DMT by CatBH and subsequent steps including dehydrocoupling and displacement of CatBAr. The research also provided insight into a possible decomposition pathway of the catalyst involving boron to zinc hydride transfer.
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Erika M. Roberts, Fedor M. Miloserdov, Victor Varela-Izquierdo, Mary F. Mahon, Michael K. Whittlesey
Summary: The addition of excess ZnMe2 to a mixture of [Ru(PPh3)(3)HCl] and IMes resulted in the formation of a bis-cyclometallated complex [Ru(IMes)(PPh3)(2)] 2 and a mono-cyclometallated Ru-Zn heterobimetallic complex [Ru(IMes)'(PPh3)(2)(ZnMe)] 3. Further reactions of these complexes with H-2, PhSiH3, pinacolborane, and CO were investigated. Compounds 1, 4, 5, and 6 were synthesized and structurally characterized.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kramer, Matthew R. Gyton, Itxaso Bustos, Matthew J. G. Sinclair, Sze-yin Tan, Christopher J. Wedge, Stuart A. Macgregor, Adrian B. Chaplin
Summary: One-electron oxidation of palladium(0) and platinum(0) bis(phosphine) complexes leads to the isolation of a series of linear d(9) metalloradicals [M(PR3)(2)](+) (M = Pd, Pt; R = tBu, Ad), which can remain stable in 1,2-difluorobenzene solution for more than a day at room temperature when combined with the weakly coordinating [BArF(4)](-) counterion. The stability of the metalloradicals decreases in THF, with [Pt(PtBu3)(2)](+) exhibiting the fastest conversion into platinum(II) complexes. The reactions of the metalloradicals with 9,10-dihydroanthracene provide experimental evidence for the C-H bond activation mechanism of platinum. Evaluation: 8 points.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Emmanouil Broumidis, Christopher G. Thomson, Brendan Gallagher, Lia Sotorrios, Kenneth G. Mckendrick, Stuart A. Macgregor, Martin J. Paterson, Janet E. Lovett, Gareth O. Lloyd, Georgina M. Rosair, Andreas S. Kalogirou, Panayiotis A. Koutentis, Filipe Vilela
Summary: This study discovered that 1,2,6-thiadiazines can be converted into 1,2,5-thiadiazole 1-oxides using visible light and oxygen under ambient conditions, which was previously difficult to achieve. Experimental and theoretical studies revealed that 1,2,6-thiadiazines act as triplet photosensitizers and undergo a selective cycloaddition reaction to form an endoperoxide.
Article
Chemistry, Physical
Matthew J. Andrews, Ambre Carpentier, Alexandra M. Z. Slawin, David B. Cordes, Stuart A. Macgregor, Allan J. B. Watson
Summary: We present a comprehensive study on the mechanism of Cu-catalyzed arylboronic acid iododeboronation reaction, combining experimental and computational analysis. Through structural and DFT analysis, we have identified the reaction precatalyst and gained insight into each step of the catalytic cycle. Important findings include the role of the ligand stoichiometry in turnover events, H-bonding facilitated transmetalation, and the integral involvement of the ligand in oxidative events. These results provide a framework for understanding the impact of ligands on Cu-mediated oxidative coupling reactions.
Article
Chemistry, Physical
Matthew Wheatley, Marco Zuccarello, Maria Tsitopoulou, Stuart A. Macgregor, Olivier Baudoin
Summary: In this study, mechanistic investigations were conducted on the reactivity of various alpha-substituted C(sp(3))-H bonds in the context of Pd-0-catalyzed C(sp(3))-H arylation. The results provide important insights into the reaction kinetics and a reactivity scale was determined, which will be useful for future studies in transition-metal-catalyzed C(sp(3))-H activation.
Article
Chemistry, Multidisciplinary
Joe C. Goodall, M. Arif Sajjad, Emily A. Thompson, Samuel J. Page, Adam M. Kerrigan, Huw T. Jenkins, Jason M. Lynam, Stuart A. Macgregor, Andrew S. Weller
Summary: The group 7 complexes [M(& kappa;(3)-2,6-(R2PO)(2)C5H3N)(CO)(2)L][BAr4F] [M = Mn, R = Pr-i, L = THF; M = Re, R = Bu-t, L = vacant site] undergo solid-gas reactivity with CO in the crystals to form THF substitution products or CO addition products. The [BAr4F] anions show large, local, adaptive changes for M = Mn, while the changes are smaller and remote to the site of reactivity for M = Re.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Matthew E. Grundy, Lia Sotorrios, Milan Kumar Bisai, Kang Yuan, Stuart A. Macgregor, Michael J. Ingleson
Summary: This article reports the synthesis of (NacNac)Zn(DMT) complex via two different routes and its use as a catalyst for C-H borylation. Computational studies elucidated the reaction mechanism and revealed the influence of the electronic and steric parameters of the base on the catalyst's performance.
