Article
Chemistry, Multidisciplinary
Chamila Manankandayalage, Daniel K. Unruh, Clemens Krempner
Summary: The intramolecular inverse frustrated Lewis pairs (FLPs) with weakly Lewis acidic boryl and strongly basic guanidino moieties were synthesized and characterized, demonstrating their capability to activate small molecules. These novel FLPs show promising potential in diverse chemical transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Ting Chen, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: This study investigates the properties of the products formed by the reaction between PAr3/B(C6F5)(3) and DEAD. It is found that the steric demands and electronic structures play a crucial role in determining the nature of the products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Ting Chen, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: In this work, we reported the reactions of phosphine/borane FLPs with chlorodiazirines, which resulted in the reduction of the N=N double bond and formation of phosphinimide/amidoborate zwitterions. A mechanistic study using DFT showed that these reactions proceed through FLP addition and subsequent group transfer reactions to nitrogen, followed by the capture of a halide anion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Zhipeng Lu, Minsoo Ju, Yi Wang, Jonathan M. Meinhardt, Jesus I. Martinez Alvarado, Elisia Villemure, Jack A. Terrett, Song Lin
Summary: This study demonstrates the functionalization of C(sp(3))-H bonds using frustrated radical pairs (FRPs) generated from disilazide donors and an N-oxoammonium acceptor. The FRPs cleave unactivated C-H bonds to provide aminoxylated products, and the reaction selectivity towards tertiary, secondary, or primary C-H bonds can be controlled by tuning the structure of the donor. Mechanistic studies confirm the formation and involvement of radical pairs in the target reaction.
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Lei Qin, Zhaoyin Zhang, Ruiqin Liu, Ming Zhou, Lili Zhao
Summary: DFT calculations were used to investigate the mechanism of S-S bond cleavage in disulfides by a frustrated Lewis pair. The calculations revealed that the reaction proceeds through the formation of a weak complex between the disulfide and the Lewis acid. The S-S bond can be activated by the Lewis base leading to its cleavage and the formation of the desired product. The mechanism was compared to that of H-H bond cleavages and it was found that a weak donor-acceptor complex is formed before S-S bond cleavage.
TETRAHEDRON LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Ayan Dasgupta, Emma Richards, Rebecca L. Melen
Summary: Progress in frustrated Lewis pair (FLP) chemistry has highlighted the significance of main group elements in catalysis, introducing novel approaches to synthetic chemistry. Recent studies have uncovered new reactivities of frustrated Lewis pairs involving single-electron transfer processes, leading to the formation of reactive frustrated radical pairs (FRP). Electron Paramagnetic Resonance (EPR) spectroscopy has been employed to explain the nature and stability of the observed radical species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yoichi Hoshimoto, Mahiro Sakuraba, Takuya Kinoshita, Masaki Ohbo, Manussada Ratanasak, Jun-ya Hasegawa, Sensuke Ogoshi
Summary: This study reports a mechanism for the revival of frustrated carbene-borane pairs in an external-stimuli responsive system, involving thermal-induced borane transfer and conformational isomerization to cleave H-2. The pathway mediated by boron-jumping and dynamic conformational isomerization is supported by combined experimental and theoretical studies.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lei Li, Wenxiu Liu, Runhua Chen, Shu Shang, Xiaodong Zhang, Hui Wang, Hongjun Zhang, Bangjiao Ye, Yi Xie
Summary: The efficient chemical conversion of CO2 to DMC was achieved by constructing FLP sites, and the reaction mechanism on these sites was systematically investigated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jorge Juan Cabrera-Trujillo, Israel Fernandez
Summary: This study computationally explored the activation of a single C-F bond in di- and trifluoromethyl groups by frustrated Lewis pairs (FLPs), revealing a unique cooperative action by the FLP partners. The process proceeds through the intermediacy of a rare hypervalent species featuring a pentacoordinate carbon atom.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Zhen Wan, Chengjun Wang, Chun Yang, Dongge Ma, Hongwei Ji, Chuncheng Chen, Wanhong Ma, Jincai Zhao
Summary: In this study, an unusual inverse H-transfer order is reported, where photoinduced solid In2O3-FLPs catalyze the hydrogenated dehalogenation of aryl halides. The results show that this method effectively activates the aryl halides and performs the dehalogenation reaction with high yields. By studying the H/D kinetic isotope effects and activation energies of hydrogenated dehalogenation, it is demonstrated that the initial hydride transfer mediated by photoinduced solid FLPs is more effective than common proton transfer.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Thermodynamics
Yuxiang Zhu, Chong-Wen Zhou, Alexander A. Konnov
Summary: In this study, the reaction kinetics of hydrogen-abstraction reactions from methoxymethanol by various radicals were investigated using high-level ab initio calculations. It was found that the H-abstraction reactions from the secondary carbon atom of methoxymethanol are favored pathways. Different radicals have different rate constants for hydrogen-abstraction reactions at different temperatures.
COMBUSTION AND FLAME
(2021)
Article
Chemistry, Multidisciplinary
Elena S. Osipova, Ekaterina S. Gulyaeva, Evgenii I. Gutsul, Vladislava A. Kirkina, Alexander A. Pavlov, Yulia V. Nelyubina, Andrea Rossin, Maurizio Peruzzini, Lina M. Epstein, Natalia V. Belkova, Oleg A. Filippov, Elena S. Shubina
Summary: The reaction between basic [(PCP)Pd(H)] and acidic [LWH(CO)(3)] leads to the formation of bimolecular complexes that catalyze dehydrogenation. Experimental and computational studies reveal the formation of a complex in the first step, where proton transfer is the rate-determining step.
Article
Chemistry, Organic
Hong-Gang Cheng, Maoping Pu, Gourab Kundu, Franziska Schoenebeck
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Minh Hieu Nguyen, Maoping Pu, Luoqiang Zhang, Yonggui Robin Chi, Yun-Dong Wu, Jianrong Steve Zhou
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Siqi Liu, Maoping Pu, Yun-Dong Wu, Xinhao Zhang
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Shenghan Teng, Yonggui Robin Chi, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Jianrong Steve Zhou
Summary: The nickel-catalyzed intermolecular Heck reaction of cycloalkenes with aryl triflates, mesylates, and tosylates shows excellent enantiomeric ratios. Additionally, the asymmetric reductive Heck reaction is also applicable to a 2-cyclopentenone ketal, equivalent to conjugate arylation of the enone itself.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Fei Tan, Maoping Pu, Jun He, Jinzhao Li, Jian Yang, Shunxi Dong, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study describes an enantioselective homologation of ketones with alpha-alkyl alpha-diazo esters using a chiral scandium(III) N,N'-dioxide catalyst to produce a series of optically active beta-keto esters with an all-carbon quaternary center. This method provides a highly selective and synthetically efficient strategy for the synthesis of enantioenriched compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wei Yang, Maoping Pu, Xiaobin Lin, Min Chen, Yanji Song, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: In this study, a novel method was developed for the synthesis of vinyl gamma-amino amides with high gamma-selectivity and enantioselectivity using a high-spin chiral complex catalyst. The calculation showed a spin state change from quartet cobalt(II) complex to doublet Co(II)-carbene species for Z-selective and enantioselective nucleophilic addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wen Liu, Maoping Pu, Jun He, Tinghui Zhang, Shunxi Dong, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study presents an efficient enantioselective radical carboazidation and diazidation reaction of α,β-unsaturated ketones and amides catalyzed by chiral N,N'-dioxide/Fe(OTf)(2) complexes, enabling the preparation of chiral compounds from substituted alkenes. Control experiments and mechanistic studies confirmed the radical pathway in the reaction process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Daoyong Zhu, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: This study revealed that palladium catalyzes a domino Heck arylation and alkylation of nonconjugated cyclodienes to produce trans isomers of disubstituted cyclohexenes with exceptionally high enantiomeric ratios. Through DFT calculations and experiments, it was demonstrated that the interaction between the two CF bonds of Josiphos and the sodium ion of malonates facilitates stereoselective allylic attack. This represents a new type of attractive noncovalent interactions discovered in organometallic catalysis.
Article
Chemistry, Multidisciplinary
Long Chen, Maoping Pu, Shiyang Li, Xinpeng Sang, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: The construction of quaternary carbon centers with chiral selectivity is a significant challenge in asymmetric catalysis research. Using a chiral N,N'-dioxide-Co(II) complex, an efficient enantioselective Michael reaction was achieved for the synthesis of nitrile-, aryl-, and dialkyl-bearing carbon centers, with applications in the divergent synthesis of pharmaceuticals and natural products. The through-space dispersion interactions between unbound silyl ketene imines and the 1-acrylpyrazole-bonded catalyst are crucial for facilitating the reactivity and enantioselectivity of the process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaobin Lin, Maoping Pu, Xinpeng Sang, Shiyang Li, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study reports the enantioselective cycloaddition reaction between thioketones and alpha-diazo pyrazoleamides, leading to the direct synthesis of tetrasubstituted thiiranes, which can be further transformed into tetrasubstituted olefins through desulfuration. The reaction is catalyzed by chiral N,N'-dioxide/cobalt(II) complexes and exhibits high efficiency and stereoselectivity. This work provides a route for selectively constructing challenging compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Luoqiang Zhang, Xiuhua Wang, Maoping Pu, Caiyou Chen, Peng Yang, Yun-Dong Wu, Yonggui Robin Chi
Summary: Nickel catalysts with chiral pyrox ligands were used for enantioselective reductive arylation and heteroarylation of aldimines using (hetero)aryl halides and sulfonates. Crude aldimines generated from the condensation of aldehydes and azaaryl amines can also be used for catalytic arylation. The mechanism involves an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines, as supported by density functional theory (DFT) calculations and experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qianwen He, Mao-Ping Pu, Zheng Jiang, Hongyu Wang, Xiaoming Feng, Xiaohua Liu
Summary: A chiral cobalt complex was reported as a catalyst for the enantioselective epoxidation of cyclic and acyclic trisubstituted alkenes. The chiral complex played a crucial role in the formation of Co-O intermediate and enantioselective electrophilic oxygen transfer. Mechanistic studies and DFT calculations confirmed the formation of Co-O species as a quartet Co(III)-oxyl tautomer. The origin of enantioselectivity was elucidated through control experiments, nonlinear effects, kinetic studies, and DFT calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Guihua Pan, Maoping Pu, Hongyu Wang, Meijia Ying, Yi Li, Shunxi Dong, Xiaoming Feng, Xiaohua Liu
Summary: A solid-liquid phase-transfer strategy was devised to control the generation speed of arynes, enabling a catalytic enantioselective nucleophilic addition reaction with good stereoselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Tinghui Zhang, Ziwei Zhong, Zi Zeng, Zitong Zhu, Fei Wang, Yuxin Zhang, Xiaohua Liu, Maoping Pu, Xiaoming Feng
Summary: The asymmetric synthesis of enantioenriched C3-arylated oxindoles has been achieved via the Friedel-Crafts alkylation of 3-bromo-3-substituted oxindoles with arenes and heteroarenes, using a chiral N,N'-dioxide/transition metal complex as the catalyst.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Thomas Scattolin, Maoping Pu, Franziska Schoenebeck
CHEMISTRY-A EUROPEAN JOURNAL
(2018)