Review
Chemistry, Multidisciplinary
Heng Wang, Jialin Wen, Xumu Zhang
Summary: Asymmetric hydrogenation of double bonds is an effective method for preparing chiral molecules, with noble metals and bidentate ligands showing remarkable reactivity. The development of chiral tridentate ligands has become increasingly important, enabling both reactivities and stereoselectivities in asymmetric hydrogenation. While noble metal catalysts with chiral tridentate ligands have made significant achievements, there is still a high demand for designing chiral tridentate ligands for earth abundant metal catalysts.
Article
Chemistry, Inorganic & Nuclear
J. I. Badillo-Gomez, E. P. Sanchez-Rodriguez, R. A. Toscano, M. Gouygou, M. C. Ortega-Alfaro, J. G. Lopez-Cortes
Summary: A new phosphine-free [N,N,O]-tridentate Schiff base ligand L1 was synthesized using 2-Ferrocenyl-2-thiazoline as scaffold. The ligand was successfully obtained with an overall yield of 83% after two-step synthesis. L1 showed good coordination ability towards Ru(II) and exhibited moderate to excellent catalytic performance in transfer hydrogenation of various substrates.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Elizabeth M. Bolitho, Nathan G. Worby, James P. C. Coverdale, Juliusz A. Wolny, Volker Schuenemann, Peter J. Sadler
Summary: Organo-osmium(II) complexes catalyze the reduction of prochiral ketones to optically pure alcohols with high efficiency and enantioselectivity. These complexes also exhibit high turnover frequencies and conversions for the asymmetric transfer hydrogenation of acetophenone-derived substrates.
Article
Chemistry, Organic
Jia-Yin Wang, Guigen Li, Wen-Juan Hao, Bo Jiang
Summary: A new asymmetric catalytic conjugate reduction method has been established for synthesizing enantioenriched cyclobuta[a]-naphthalen-4(2H)-ones using copper-bisphosphine complexes as catalysts, providing excellent regio- and enantioselectivities. This protocol is tolerant to a broad scope of substrates, exhibits high compatibility with various substituents, and offers excellent stereoselectivity.
Article
Chemistry, Organic
Dawei Gong, Degong Kong, Yufei Li, Caiyu Gao, Lina Zhao
Summary: A nickel-catalyzed semihydrogenation of azoarenes to hydrazoarenes with NH3BH3 is developed, exhibiting good functional group tolerance and a high turnover frequency at room temperature. Control and deuterium-labeling experiments reveal that the ethanol hydroxyl and BH3 groups each donated one hydrogen, resulting in the formation of B-(OEt)(3) and H-2 as main byproducts. Density functional theory calculations suggest a ligand-to-ligand hydrogen transfer mechanism for the reaction. This study presents a novel nickel catalytic system for the semihydrogenation of azoarenes.
Article
Chemistry, Applied
Robert T. Kumah, Stephen O. Ojwach
Summary: In this study, a series of dinuclear piano-stool ruthenium (II) complexes were synthesized and their structures were confirmed using various analytical techniques. The catalytic performances of these complexes in transfer hydrogenation reactions were investigated, and the results showed that they exhibited high catalytic activities and could efficiently catalyze a broad range of ketones at low catalyst loadings.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Shubhadeep Chandra, Ola Kelm, Uta Albold, Arijit Singha Hazari, Damijana Urankar, Janez Kosmrlj, Biprajit Sarkar
Summary: Azocarboxamides, a special class of azo ligands, exhibit intriguing electronic properties due to their versatile binding modes and coordination flexibility, which may have significant implications for homogeneous catalysis. The investigation showed that different coordination motifs of the ligand influence catalytic activity, and C-H activation in azocarboxamide ligands is reported for the first time.
Article
Chemistry, Multidisciplinary
Xintuo Yang, Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. The (EtO)(2)MeSiH/BQ redox system is crucial for the highly selective and efficient hydrooxygenation, where alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides an efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Yunfan Yue, Tian Ma, Hexiang Qi, Yaqi Zhao, Xiaofan Shi, Yanhui Tang, Min Pu, Ming Lei
Summary: In this study, a series of bowl-shaped quadridentate ligands and their manganese catalysts were designed for the hydrogenation of unsaturated bonds using density functional theory. The calculated results suggest that the bowl-shaped structure of the ligands and their connection to the Si-N-Si-C-Si-C six-membered ring core significantly affect the catalytic activity and selectivity. This work provides theoretical insights for designing new transition metal catalysts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Zheng Wang, Ning Ma, Xiaochi Lu, Ming Liu, Tian Liu, Qingbin Liu, Gregory A. Solan, Wen-Hua Sun
Summary: A series of manganese(i) carbonyl complexes with structurally related NN- and NNN-chelating ligands were synthesized and used as catalysts for transfer hydrogenation. The NN-systems based on N-R functionalized 5,6,7,8-tetrahydroquinoline-8-amines showed the highest catalytic activity in the conversion of acetophenone to 1-phenylethanol. The N-isopropyl derivative, Mn1, when combined with t-BuONa, achieved efficient reduction of acetophenone and various carbonyl substrates, with high TON values (up to 17,200; TOF of 3550 h(-1)). These findings support an outer-sphere mechanism for the hydrogen transfer and provide a sustainable alternative for producing alcoholic products from carbonyl substrates.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Noha Khamis, Guy J. Clarkson, Martin Wills
Summary: The synthesis of a variety of N-(heterocyclesulfonyl)-functionalized Noyori-Ikariya catalysts was described in this study. These complexes were prepared from C2-symmetric 1,2-diphenylethylene-1,2-diamine (DPEN) and characterized using multiple methods including X-ray crystallography. The complexes exhibited catalytic activity in the asymmetric transfer hydrogenation (ATH) of various acetophenone derivatives, yielding products with high enantioselectivity in most cases, especially for ortho-substituted acetophenones.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
M. C. Joseph, A. J. Swarts, S. F. Mapolie
Summary: A series of novel cationic ruthenium half-sandwich complexes with 1-substituted-4-pyridyl-1H-1,2,3-triazole ligands were synthesized and found to be efficient catalyst precursors for transfer hydrogenation reactions. With a low concentration of base, these complexes could hydrogenate acetophenone with excellent conversions within a short reaction time. The catalytic efficiency of the most effective catalyst was further demonstrated in the transfer hydrogenation of a small library of ketones.
Article
Multidisciplinary Sciences
Bram B. C. Peters, Jia Zheng, Norman Birke, Thishana Singh, Pher G. Andersson
Summary: The authors developed a general iridium-catalyzed enantioconvergent hydrogenation method for a broad range of functionalized trisubstituted olefins. This method allows for efficient introduction of chirality into non-chiral substrates. The significance of this method lies in its ability to hydrogenate both isomerically pure alkenes and mixtures to yield the same major enantiomer in excellent enantiomeric excess, which is unusual in transition-metal catalyzed asymmetric hydrogenations.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Danielle L. J. Pinheiro, Martin Nielsen
Summary: The chemoselective reduction of enamides to alpha-amino acids using Ru pincer complexes as catalysts and iPrOH and EtOH as H-donors and solvents is demonstrated. A range of alpha-amino acids is synthesized with good to excellent yields. Applications, large-scale synthesis, and a one-pot experiment are also reported. Deuterium-labeling experiments show high regioselectivity between the alpha- and beta-positions of the alkene unit.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Feng Chen, Isolda Romero-Canelon, Abraha Habtemariam, Ji-Inn Song, Samya Banerjee, Guy J. Clarkson, Lijiang Song, Ivan Prokes, Peter J. Sadler
Summary: We synthesized a series of novel substituted sulfonyl ethylenediamine (en) Ru-II arene complexes, which showed antiproliferative activity against cancer cells and exhibited catalytic activity in transfer hydrogenation reactions and reactions with thiols.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Vijyesh K. Vyas, Guy J. Clarkson, Martin Wills
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Ye Zheng, Guy J. Clarkson, Martin Wills
Article
Chemistry, Organic
Shweta K. Gediya, Guy J. Clarkson, Martin Wills
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Jonathan Barrios-Rivera, Yingjian Xu, Martin Wills
Article
Chemistry, Organic
Thomas H. Hall, Hannah Adams, Vijyesh K. Vyas, K. L. Michael Chu, Martin Wills
Summary: A detailed study was conducted on the asymmetric transfer hydrogenation (ATH) of a series of enones using Ru(II) catalysts. The ATH reaction can readily discriminate between double and triple bonds adjacent to ketones, reducing the double bond but leaving a triple bond intact in the major product.
Article
Chemistry, Physical
Abigail L. Whittock, Nazia Auckloo, Adam M. Cowden, Matthew A. P. Turner, Jack M. Woolley, Martin Wills, Christophe Corre, Vasilios G. Stavros
Summary: This study investigates the ultrafast dynamics of two photoprotective compounds and reveals their relaxation and cooling processes in solution after photoexcitation. The findings shed light on the essential components of microbial life and have implications for the development of molecular photon-to-heat converters for various applications.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Organic
Vijyesh K. Vyas, Guy J. Clarkson, Martin Wills
Summary: Compounds containing bicyclo[1.1.1]pentane (BCP) adjacent to a chiral center can be prepared with high enantiomeric excess through asymmetric transfer hydrogenation (ATH) of adjacent ketones. The reduction method is applied to the synthesis of a BCP analogue of the antihistamine drug neobenodine.
Article
Chemistry, Inorganic & Nuclear
Pavel A. Dub, Nikolay Tkachenko, Vijyesh K. Vyas, Martin Wills, Justin S. Smith, Sergei Tretiak
Summary: This study reveals that there are two spatial regions of the catalyst that simultaneously control the enantioselectivity for any arbitrary substrate: the region of the (tethered) eta(6)-arene ligand and the region of the SO2 moiety. Noncovalent interactions in each region, such as CH-pi, C-H center dot center dot center dot H-C, lone pair-pi, lone pair center dot center dot center dot H-C, play a crucial role in determining the final percent enantiomeric excess (% ee).
Article
Chemistry, Physical
Ye Zheng, Jaime A. Martinez-Acosta, Mohammed Khimji, Luiz C. A. Barbosa, Guy J. Clarkson, Martin Wills
Summary: Aromatic ketones with ortho-substituents showed high enantioselectivity under asymmetric transfer hydrogenation conditions, while N-methylimidazole-containing ketones exhibited unexpected enantioselectivity switches upon variation of the opposing aromatic group. Pyrrole-containing ketones were found to be resistant to reduction in this study.
Article
Chemistry, Organic
Shweta K. Gediya, Vijyesh K. Vyas, Guy J. Clarkson, Martin Wills
Summary: The study successfully achieved the asymmetric transfer hydrogenation (ATH) of alpha-keto-1,4-diamides using a tethered Ru/TsDPEN catalyst with high enantiomeric excess. By investigating derivatives, the structural elements leading to the highest enantioselectivities in the products were identified, and the reduction products were further converted into a variety of synthetically valuable derivatives.
Article
Chemistry, Organic
Jonathan Barrios-Rivera, Yingjian Xu, Guy J. Clarkson, Martin Wills
Summary: The application of enantiomerically-pure ruthenium(II) catalysts containing N - functionalised TsDPEN ligand to the asymmetric transfer hydrogenation of 15 examples of alpha-heterocyclic acetophenone derivatives is reported, with products of up to 99% ee formed. (C) 2021 Elsevier Ltd. All rights reserved.
Article
Chemistry, Organic
Ye Zheng, Martin Wills
Summary: In this study, the reduction of Bpin-containing ketones by asymmetric transfer hydrogenation (ATH) was investigated. It was found that the reaction products exhibited high ee when the Bpin group was in the para- or meta-position.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Organic
Jonathan Barrios-Rivera, Yingjian Xu, Martin Wills, Vijyesh K. Vyas
ORGANIC CHEMISTRY FRONTIERS
(2020)
Article
Chemistry, Multidisciplinary
Conor Dean, Sundaram Rajkumar, Stefan Roesner, Nessa Carson, Guy J. Clarkson, Martin Wills, Matthew Jones, Michael Shipman
Article
Chemistry, Multidisciplinary
Richard C. Knighton, Krishna Sharma, Naomi S. Robertson, David R. Spring, Martin Wills
