Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Wang Jiang, Xiuxiu Yang, Lin Lin, Chaoguo Yan, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: Metal-catalyzed C-H activation strategies provide an efficient approach for synthesis. In this study, visible-light-induced late-stage C-H activation was achieved using a single rhodium complex. The reaction offers advantages such as environmental friendliness and the utilization of inherent directing groups, providing a new platform for ligand design and preparation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Henning Steinert, Julian Loeffler, Viktoria H. Gessner
Summary: The computational studies on ylide-substituted tetrylenes in bond activation reactions showed that boryl groups lead to beneficial properties and low barriers for single-site activation reactions. Different alpha-substituents impact the activation process, with boryl-substituted tetrylenes allowing for an additional activation pathway. The cooperative mechanisms in cyclic ylidyltetrylenes show potential for bond activations under mild conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maximilian Muhr, Raphael Buhler, Hao Liang, Jonas Gilch, Christian Jandl, Samia Kahlal, Jean-Yves Saillard, Christian Gemel, Roland A. Fischer
Summary: Treatment of [Ru(COD)(MeAllyl)(2)] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to the formation of reactive intermediates capable of activating Si-H or C-H bonds. The structures and properties of the resulting complex compounds [Ru(GaCp*)(3)(SiEt3)H-3] (1) and [Ru(GaCp*)(3)(C7H7)H-3] (2) have been investigated and characterized.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Yuliang Xu, Yizhou Yang, Yizhen Liu, Zhen Hua Li, Huadong Wang
Summary: The hydrogenolysis of C-C bonds is a crucial process in the petroleum industry, but it often requires high temperatures and pressures with limited selectivity. However, a borenium complex has been discovered to catalyze the selective hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds at ambient temperature without the need for directing groups. Mechanistic studies have revealed that the reaction involves the synergistic activation of dihydrogen by the borenium complex and alkylarenes, followed by retro-Friedel-Crafts reaction to cleave the C(aryl)-C(alkyl) bonds. The synthetic utility of this protocol has been demonstrated by converting post-consumer polystyrene into valuable benzene and phenylalkanes with a mass recovery rate of over 90%.
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
Chemistry, Multidisciplinary
Thomas Hansen, Pascal Vermeeren, F. Matthias Bickelhaupt, Trevor A. Hamlin
Summary: The alpha-effect explains the enhanced reactivity of alpha-nucleophiles compared to normal nucleophiles, but the exact origin is still debated. Our analysis found that an alpha-nucleophile needs to have a small HOMO lobe and high energy HOMO to exhibit the alpha-effect.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Milan Kumar Bisai, V. S. V. S. N. Swamy, K. Vipin Raj, Kumar Vanka, Sakya S. Sen
Summary: The reactivity of a newly reported silylene compound was investigated, resulting in a series of reactions with borane compounds and other molecules, demonstrating the ability of silylene to activate multiple small molecules and form novel coupling products.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yasuhiro Nishikawa, Daiki Mori, Mayuko Toyoda, Yukiho Amano, Midori Hosoi, Momoka Ando, Osamu Hara
Summary: A chelating hydrazone amide was reported as a protecting group for carboxylic acids. Unlike most esters, 2picolinaldehyde hydrazone amides are stable under acidic or basic hydrolytic conditions. However, they can be easily converted to carboxylic acids via Ni-mediated hydrolysis. Control experiments and peptide synthesis confirmed the orthogonal reactivities of hydrazone amides and other protecting groups, demonstrating the utility of chelating hydrazone amides as protecting groups.
Article
Chemistry, Organic
Chandan Kumar Giri, Sudeshna Mondal, Mahiuddin Baidya
Summary: A straightforward synthesis of biologically relevant dibenzo[c,h]chromen-6-one and dibenzo[c,f]chromen-5-one frameworks has been accomplished using ruthenium catalysis. The method exhibited high reaction yields, broad functional group tolerance, and scalability.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Conghui Tang, Xu Qiu, Zengrui Cheng, Ning Jiao
Summary: Molecular oxygen, as a green and non-toxic oxidant, offers various advantages in organic transformations for the synthesis of oxygen-containing compounds. Recent advances in radical processes using molecular oxygen as an oxidant have been discussed, along with reaction scopes, limitations, and mechanisms, providing insights for future developments in this field.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Jorge Juan Cabrera-Trujillo, Israel Fernandez
Summary: By means of Density Functional Theory calculations, the poorly understood factors controlling the complete meta-selectivity observed in the C-H activation reactions of alkylarenes promoted by aluminyl anions have been explored. It was found that the selectivity occurs during the initial nucleophilic addition step, where the key LP(Al)->pi*(C=C) molecular orbital interaction is more stabilizing for the meta-pathway.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dong-Liang Zhang, Zhi-Qiang Zhu, Zong-Bo Xie, Xiao-Ping Zhang, Zhang-Gao Le
Summary: A visible-light-induced organophotocatalytic reaction has been developed for high-yield synthesis of cyanoalkyl indolo[2,1-a]isoquinolinones through the reaction of cyclobutanone oxime esters with 2-aryl indole derivatives. The reaction utilizes an inexpensive photosensitizer and does not require any additives. It also allows for the incorporation of various functional groups.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Claire L. McMullin, Samuel E. Neale, Georgia L. Young
Summary: The breaking of the asymmetric B-B bond within a MgII diboranate complex in the presence of DMAP is analyzed using DFT and NBO methods. The formation of a magnesium-boryl species and its nucleophilic behavior is explored through inner and outer sphere mechanisms. The study provides insights into the mechanistic features and reactivity of the system.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
C. Christopher Almquist, Nicole Removski, Thayalan Rajeshkumar, Benjamin S. Gelfand, Laurent Maron, Warren E. Piers
Summary: This study reports the activation of ammonia through coordination to molybdenum centers. Experimental results show that (B(2)Pz(4)Py)Mo-II-NH3 loses dihydrogen at room temperature, resulting in the formation of the dinuclear compound (B(2)Pz(4)Py)Mo-N-Mo(B(2)Pz(4)Py). Mechanistic details were supported through experimental observations and density functional theory calculations, revealing the under-appreciated role of bridging nitrido intermediates in the process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dan Liu, Kai Yang, Di Fang, Shi-Jun Li, Yu Lan, Yiyun Chen
Summary: This study reports the first method for generating formyl radicals from alpha-chloro N-methoxyphthalimides, which selectively synthesize aldehydes under mild photoredox conditions. The method exhibits excellent chemoselectivity and regioselectivity for installing aldehydes on various organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tao Zhang, Kangbao Zhong, Zhi-Keng Lin, Linbin Niu, Zi-Qi Li, Ruopeng Bai, Keary M. Engle, Yu Lan
Summary: In this study, computational evidence is presented to support the role of Zn coordination in accelerating reductive elimination from Ni(II) centers in Ni-catalyzed cross-couplings. The Zn-assisted pathway was found to have lower energy compared with direct reductive elimination from a Sigma-coordinated Ni(II) intermediate. Theoretical calculations reveal a significant Z-type Ni-Zn interaction that enhances reductive elimination.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kangbao Zhong, Shihan Liu, Xiaoqian He, Hao Ni, Wei Lai, Wenting Gong, Chunhui Shan, Zhuang Zhao, Yu Lan, Ruopeng Bai
Summary: This report describes the oxidative cyclopalladation activation of a C =C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway involves an oxidative cyclopalladation to generate a pallada-cyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
CHINESE CHEMICAL LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Yumeng Shuai, Jianzhong Zhao, Renheng Bo, Yu Lan, Zengyao Lv, Yihui Zhang
Summary: Mechanically-guided three-dimensional assembly is a novel method for fabricating micro/nanoscale 3D structures and devices. It utilizes compressive buckling in a patterned high-modulus thin film integrated with a low-modulus elastomer substrate. To address the challenges of highly flexible 3D mesostructures or those with large-area suspended features, a wrinkling-assisted strategy is proposed to facilitate the delamination at desired regions. This strategy involves introducing an assisting layer with a weaker film/assisting-layer interface and utilizing wrinkles in the assisting layer to induce additional driving forces for separation.
JOURNAL OF THE MECHANICS AND PHYSICS OF SOLIDS
(2023)
Article
Chemistry, Multidisciplinary
Meng Miao, Lei Zhu, Hong Zhao, Lei Song, Si-Shun Yan, Li-Li Liao, Jian-Heng Ye, Yu Lan, Da-Gang Yu
Summary: Difunctionalizing carboxylation of alkynes with CO2 is a sustainable and important strategy to generate valuable acrylate derivatives from readily available starting materials. This study introduces a visible-light-driven and transition metal-free thio-carboxylation of alkynes with thiophenols and CO2. The use of single-electron activation of CO2 leads to unique beta-carboxylation, followed by efficient cyclizing acylation to obtain important thiochromones. The one-pot method features mild reaction conditions, high selectivity, scalability, and facile derivatization of products to bioactive compounds.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Lei Zeng, Shihan Liu, Yu Lan, Lizhu Gao
Summary: This study reports a catalytic asymmetric inverse-electron-demand oxa-Diels-Alder reaction for the synthesis of enantioenriched six-membered oxygen-containing heterocycles. The reaction between α-bromoacroleins and neutral alkenes is catalyzed by oxazaborolidinium cation 1f, leading to the formation of dihydropyrans with high yields and excellent enantioselectivities. The efficient synthesis of (+)-Centrolobine is demonstrated, highlighting the practical utility of this reaction.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Shugao Zhu, Dan Wang, Shihan Liu, Yufeng Ma, Hong Wang, Yu Lan, Ruopeng Bai, Ruwei Shen
Summary: The Pd-catalyzed reaction of 1-(2-iodophenyl)-3-arylprop-2-yn-1-ones with propargyl sulfonamide produces cyclobuta[b]naphthalen-3(1H)-ones, while the reaction with propargyl ethers affords 11H-benzo[b]fluoren-11-ones as products. Experimental and theoretical studies reveal that the former reaction proceeds through Pd-catalyzed cross-coupling, propargyl-allenyl isomerization, and [2 + 2] cycloaddition, while the latter involves Pd-catalyzed cross-coupling, propargylic Alder-ene-type reaction, and 6 pi-electrocyclization leading to the formation of [4 + 2] cycloadducts. The divergent formation of two types of allenic intermediates depending on propargylic substrates is confirmed and elucidated.
Article
Chemistry, Physical
Xinghua Wang, Kai Yang, Ya-Nan Wang, Shi-Jun Li, Donghui Wei, Yu Lan
Summary: Transition-metal-catalyzed transformation reactions of epoxides provide practical C2 synthons and a feasible strategy for catalyst-controlled divergent conversions. Understanding the crucial factors controlling chemoselectivity is key to rational design. Computational studies reveal that the chemoselective reaction can undergo a retro-[3 + 2] step or a carbonyl migration insertion step, influenced by the energy barriers and metal complexes configurations. These insights are important for understanding chemoselectivity and catalyst-controlled reactions.
Article
Multidisciplinary Sciences
Lei Peng, Zhen Zeng, Kai Li, Yidong Liu, Yu Lan, Hailong Yan
Summary: The catalytic dearomative cycloaddition of bicyclic heteroaromatics provides a rapid method for synthesizing functionalized heterocyclic molecules. This study presents a geometry-based differentiation approach to achieve regioselectivity in the cycloaddition of benzofurans and indoles. By controlling the rotation of a sigma bond at the C7 position, enantioenriched polycyclic compounds can be obtained from a racemic heterobiaryl. The mechanism of this parallel kinetic resolution was explained using density functional theory calculations. The bioactivity of the dearomatized products was evaluated, with some compounds exhibiting interesting biological activities.
Article
Chemistry, Multidisciplinary
Wenqiang Zhou, Song Xi, Haohua Chen, Dan Jiang, Jiao Yang, Shuangwei Liu, Ling He, Hanyue Qiu, Yu Lan, Min Zhang
Summary: Bridged frameworks are important in chemistry and biology, found commonly in pharmaceuticals and natural products. Traditional methods of building these rigid segments at the middle or late stage of synthesis decrease efficiency and specificity. In this study, a novel strategy was used to construct a morphan core equipped with an allene/ketone group through an enantioselective a-allenylation of ketones. The resulting bridged backbone guided the assembly of up to five fusing rings, and the allene and ketone groups allowed precise installation of various functionalities, leading to a concise total synthesis of nine strychnan alkaloids.
Article
Chemistry, Organic
Xingwei Li, Runze Zhang, Zisong Qi, Junwei Li, Lingheng Kong
Summary: Regio- and chemoselective amidation of benzocyclobutenols has been achieved using dioxazolone as the amidating reagent and cobalt(III) or rhodium(III) catalysts. The cobalt(III)-catalyzed coupling first forms an isolable o-(N-acylamino)arylmethyl ketone, which can further cyclize to indole derivatives. In contrast, efficient stepwise diamidation is achieved under rhodium(III) catalyst control. The chemoselectivity is controlled by the catalyst and reaction conditions.
Article
Chemistry, Organic
Danqing Ji, Zisong Qi, Xingwei Li
Summary: In this study, a straightforward and efficient enantioselective hydrophosphination of gem-difluoroallenes using disubstituted phosphines was developed. A wide range of enantioenriched fluorinated allylic phosphines were successfully synthesized with excellent regio- and enantioselectivity, demonstrating their potential for synthetic and catalytic applications.
Article
Chemistry, Physical
Xingchen Liu, Haohua Chen, Dali Yang, Binjing Hu, Ying Hu, Shengchun Wang, Yu Lan, Aiwen Lei, Jie Li
Summary: A multicomponent sulfonylation reaction using sulfonyl chlorides and OPiv-supported organozinc reagents was achieved via cobalt-catalyzed alkene difunctionalizations. Anion-coordination played a critical role in modifying the reactivity and chemical properties of organozinc reagents. The OPiv-coordination resulted in the lower reducibility of arylzinc pivalates, allowing for the in situ formation of catalytically relevant Co(I) species as the active catalyst in carbosulfonylation reactions.
Article
Multidisciplinary Sciences
Ying Hu, Jiali Peng, Binjing Hu, Jixin Wang, Jing Jing, Jie Lin, Xingchen Liu, Xiaotian Qi, Jie Li
Summary: The authors present a cobalt-catalyzed synthesis of tri- and tetrasubstituted alkenyl silanes and stannanes via C-O functionalization of vinyl acetates using silylzinc pivalate and stannylzinc chloride as nucleophiles. This reaction is challenging but has significant importance in synthetic organic chemistry.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yaling Huang, Zisong Qi, Xingwei Li
Summary: This study presents a rhodium-catalyzed highly enantioselective reaction, which enables the access to functionalized indoles with excellent enantioselectivities through the nucleophilic cyclization of 2-alkynylanilines.