Fabricating Industry‐Compatible Olefin‐Linked COF Resins for Oxoanion Pollutant ScavengingZhang, Penghui; Wang, Zhifang; Wang, Sa; Wang, Jian; Liu, Jinjin; Wang, Ting; Chen, Yao; Cheng, Peng; Zhang, Zhenjie
doi: 10.1002/anie.202213247pmid: 36300874
Large‐scale and low‐cost synthesis of covalent organic frameworks (COFs) to meet the demands of industrial application remains formidably challenge. Here we report using 2,4,6‐collidine as monomer to produce a series of highly crystalline olefin‐linked COFs by a melt polymerization method. This method enables the kilogram‐scale fabrication of self‐shaped monolithic robust foams. The afforded COFs possess extremely low cost (<50 USD/kg), superior to all the reported COFs. Furthermore, using one‐pot or post‐modification methods can conveniently transform neutral COFs to ionic COFs, which can be applied as highly efficient ion‐exchange sorbents for scavenging oxoanion pollutants. Remarkably, the superior adsorption capacity of a model oxoanion (ReO4−) is the highest among crystalline porous materials reported so far. This work not only expands the scopes of olefin‐linked COFs but also enlightens the route for the industrial production of crystalline ion exchange sorbents.
The Anionic Chemistry in Regulating the Reductive Stability of Electrolytes for Lithium Metal BatteriesYao, Nan; Sun, Shu‐Yu; Chen, Xiang; Zhang, Xue‐Qiang; Shen, Xin; Fu, Zhong‐Heng; Zhang, Rui; Zhang, Qiang
doi: 10.1002/anie.202210859pmid: 36314987
Advanced electrolyte design is essential for building high‐energy‐density lithium (Li) batteries, and introducing anions into the Li+ solvation sheaths has been widely demonstrated as a promising strategy. However, a fundamental understanding of the critical role of anions in such electrolytes is very lacking. Herein, the anionic chemistry in regulating the electrolyte structure and stability is probed by combining computational and experimental approaches. Based on a comprehensive analysis of the lowest unoccupied molecular orbitals, the solvents and anions in Li+ solvation sheaths exhibit enhanced and decreased reductive stability compared with free counterparts, respectively, which agrees with both calculated and experimental results of reduction potentials. Accordingly, new strategies are proposed to build stable electrolytes based on the established anionic chemistry. This work unveils the mysterious anionic chemistry in regulating the structure–function relationship of electrolytes and contributes to a rational design of advanced electrolytes for practical Li metal batteries.
Synthesis and Application of Alkali Metal Antimonide—A New Approach to Antimony ChemistryDollberg, Kevin; Schneider, Selina; Richter, Roman‐Malte; Dunaj, Tobias; Hänisch, Carsten
doi: 10.1002/anie.202213098pmid: 36301563
Alkali metal dihydrogen‐antimonides [M(L)xSbH2], short: alkali metal antimonides (M=Li, Na, K, Rb, Cs; 1: L=pmdta; 2: L=crown‐ether), were prepared from stibine and n‐Butyllithium, M(hmds) (hmds=hexamethyldisilazane) or MOtBu, respectively. We developed a generally applicable synthesis route for these compounds and the obtained compounds were examined on their stability depending on the alkali metal and stabilizing additives used, whereby the use of appropriate crown‐ethers allowed their isolation and characterization at room temperature. Moreover, the 1,4‐dioxane adduct [Na(dioxane)xSbH2] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me3Si)3SiSbH2 (3) which was characterized by NMR and IR spectroscopy. Reaction of 3 with (Dipp2NacNac)Ga (Dipp2NacNac=HC{C(Me)N(Dipp)}2; Dipp=2,6‐iPr2C6H3) resulted in the formation of (Dipp2NacNac)GaH(SbHSi(SiMe3)3) (4) which was furthermore characterized by single crystal x‐ray diffraction.
Native Amide‐Directed C(sp3)−H Amidation Enabled by Electron‐Deficient RhIII Catalyst and Electron‐Deficient 2‐Pyridone LigandWakikawa, Takumi; Sekine, Daichi; Murata, Yuta; Bunno, Youka; Kojima, Masahiro; Nagashima, Yuki; Tanaka, Ken; Yoshino, Tatsuhiko; Matsunaga, Shigeki
doi: 10.1002/anie.202213659pmid: 36305194
Trivalent group‐9 metal catalysts with a cyclopentadienyl‐type ligand (CpMIII; M=Co, Rh, Ir, Cp=cyclopentadienyl) have been widely used for directed C−H functionalizations, albeit that their application to challenging C(sp3)−H functionalizations suffers from the limitations of the available directing groups. In this report, we describe directed C(sp3)−H amidation reactions of simple amide substrates with a variety of substituents. The combination of an electron‐deficient CpERh catalyst (CpE=1,3‐bis(ethoxycarbonyl)‐substituted Cp) and an electron‐deficient 2‐pyridone ligand is essential for high reactivity.
Dithiol‐Activated Bioorthogonal Chemistry for Endoplasmic Reticulum‐Targeted Synergistic ChemophototherapySun, Jian; Zhang, Xiaoran; Wang, Xia; Peng, Jinlei; Song, Gang; Di, Yufei; Feng, Fude; Wang, Shu
doi: 10.1002/anie.202213765pmid: 36342403
The controlled intracellular release of nitrite is still an unmet challenge due to the lack of bio‐friendly donors, and the antitumor effect of nitrite is limited by its physiologically inert activity. Herein, we designed benzothiadiazole‐based organic nitrite donors that are stable against bio‐relevant species but selectively respond to dithiol species through SNAr/intramolecular cyclization tandem reactions in the aqueous media. The bioorthogonal system was established to target the endoplasmic reticulum (ER) of liver cancer HepG2 cells. The nitrite and nonivamide were coupled to induce elevation of intracellular levels of calcium ions as well as reactive oxygen/nitrogen species, which resulted in ER stress and mitochondrial dysfunction. We demonstrated that a combination of photoactivation and “click to release” strategy could enhance antitumor effect in cellular level and show good potential for cancer precision therapy.
Deaminative Arylation and Alkenyaltion of Aliphatic Tertiary Amines with Aryl and Alkenylboronic Acids via Nitrogen YlidesSu, Jianke; Li, Chengbo; Hu, Xinyuan; Guo, Yu; Song, Qiuling
doi: 10.1002/anie.202212740pmid: 36314477
Transition‐metal‐catalyzed Suzuki–Miyaura coupling has significantly advanced C−C bond formation and has been well recognized in organic synthesis, pharmaceuticals, materials science and other fields. In this rapid development, cross coupling without transition metal catalyst is a big challenge in this field, and using widely existing tertiary amines as electrophiles to directly couple with boronic acids has great hurdles yet significant application prospects. Herein, we report an efficient and general deaminative arylation and alkenylation of tertiary amines (propargyl amines, allyl amines and 1H‐indol‐3‐yl methane amines) with ary and alkenylboronic acids enabled by difluorocarbene under transition‐metal‐free conditions. Preliminary mechanism experiments suggest that in situ formed difluoromethyl quaternary amine salt, nitrogen ylide and tetracoordinate boron species are the key intermediates, the subsequent 1,2‐metallate shift and protodeboronation complete the new coupling reaction.
Organocatalyzed Controlled Radical Copolymerization toward Hybrid Functional Fluoropolymers Driven by LightZeng, Yang; Quan, Qinzhi; Wen, Peng; Zhang, Zexi; Chen, Mao
doi: 10.1002/anie.202215628pmid: 36329621
Photo‐controlled polymerizations are attractive to tailor macromolecules of complex compositions with spatiotemporal regulation. In this work, with a convenient synthesis for trifluorovinyl boronic ester (TFVB), we report a light‐driven organocatalyzed copolymerization of vinyl monomers and TFVB for the first time, which enabled the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain‐end fidelity. The good behaviors of “ON/OFF” switch, chain‐extension polymerizations and post‐modifications further highlight the versatility and reliability of this copolymerization. Furthermore, we demonstrate that the combination of fluorine and boron could furnish copolymer electrolytes of high lithium‐ion transference number (up to 0.83), bringing new opportunities of engineering high‐performance materials for energy storage purposes.
Mechanism‐Guided Computational Design of ω‐Transaminase by Reprograming of High‐Energy‐Barrier StepsYang, Lin; Zhang, Kaiyue; Xu, Meng; Xie, Youyu; Meng, Xiangqi; Wang, Hualei; Wei, Dongzhi
doi: 10.1002/anie.202212555pmid: 36300723
ω‐Transaminases (ω‐TAs) show considerable potential for the synthesis of chiral amines. However, their low catalytic efficiency towards bulky substrates limits their application, and complicated catalytic mechanisms prevent precise enzyme design. Herein, we address this challenge using a mechanism‐guided computational enzyme design strategy by reprograming the transition and ground states in key reaction steps. The common features among the three high‐energy‐barrier steps responsible for the low catalytic efficiency were revealed using quantum mechanics (QM). Five key residues were simultaneously tailored to stabilize the rate‐limiting transition state with the aid of the Rosetta design. The 14 top‐ranked variants showed 16.9–143‐fold improved catalytic activity. The catalytic efficiency of the best variant, M9 (Q25F/M60W/W64F/I266A), was significantly increased, with a 1660‐fold increase in kcat/Km and a 1.5–26.8‐fold increase in turnover number (TON) towards various indanone derivatives.