查看更多>>摘要:Molecular ferroelectrics have attracted tremendous attention in the past decades due to their excellent ferroelectric performance and superiorities of easy processability,mechanical flexibility,and good biocompatibility.However,the discovery of molecular ferro-electrics is a great challenge and has long relied on blind search.This situation changed recently,with the development of ferroelec-trochemistry proposed by our group.As a major design approach in ferroelectrochemistry,introducing homochirality,which facili-tates the crystallization of materials in polar crystallographic point groups,greatly improves the probability of being ferroelectrics.Various new molecular ferroelectrics with splendid properties have been precisely synthesized by using this efficient and universal strategy.In this review,we summarize the advances in the chemical design of molecular ferroelectrics through the strategy of intro-ducing homochirality.
查看更多>>摘要:The deuteration of organic compounds has attracted more attentions in recent years for the potential applications in new drug dis-covery and synthetic chemistry.For this purpose,many efficient deuterium labeling methodologies have been developed,including hydrogen isotope exchange(HIE),reductive deuteration,and dehalogenative deuteration that allow for the synthesis of selectively deuterated compounds.In the last few years,great breakthroughs in selective isotope labeling have been achieved and the interest in new methodologies for the deuteration of organic molecules is rising.In this review,we summarized the recent developments in the selective deuteration of organic molecules since 2021.Several types of key processes in deuterium incorporation reactions,in-cluding H/D exchange,reductive deuteration and dehalogenative deuteration,are introduced and discussed.
查看更多>>摘要:Frustrated Lewis Pairs(FLPs)represent a unique class of interactions in Lewis acid-base chemistry,driven by spatial hindrance or in-congruent orbital energy levels that hinder the formation of effective coordination bonds.FLPs have received significant attention for their application in activating small molecules and facilitating organic synthesis reactions.Recent developments have led to the emergence of Frustrated Radical Pairs(FRPs)as an extension of the radical family.FRPs are formed from FLPs through Single Electron Transfer(SET)and exhibit the ability to activate a variety of chemical bonds.While research on FLPs is well-established,investiga-tions into FRPs in organic reactions remain limited.This review highlights the current state of FRPs in organic synthesis,delves into mechanistic insights,explores their potential,and underscores the challenges in this emerging field.
查看更多>>摘要:As a versatile earth-abundant transition metal,Cu has long been widely applied in the C-C and C-X bond forming reactions.As for now,low-valent Cu(Ⅰ)is known to reduce the redox active electrophiles via an SET pathway to give the corresponding radical and Cu(Ⅱ)species.The resulting Cu(Ⅱ)species can interact with the radical via the out-sphere pathway,affording the coupling product.Alternatively,Cu(Ⅱ)can trap the radical through the inner-sphere process to generate Cu(Ⅲ)species and then realize challenging bond formations due to the facile reductive elimination of Cu(Ⅲ)intermediate.Although copper catalysis has been widely applied in arylations of various nucleophiles,copper-catalyzed enantioconvergent nucleophilic substitutions of racemic alkyl electrophiles have been less explored,likely due to the difficulties in overcoming the reduction potential of alkyl electrophiles,elimination of side reac-tions,and enantiomeric control.In order to overcome the high reduction potential of alkyl electrophiles,the photo-induced strategy has been developed under mild conditions.An alternative strategy with new anionic tridentate ligands has also been reported in this regard.This review summarizes recent developments in copper-catalyzed enantioconvergent nucleophilic substitutions of alkyl elec-trophiles by various nucleophiles to realize C-N,C-C,C-B,C-P and C-O bond formations and their brief mechanistic studies.
查看更多>>摘要:Tumor stroma composing diverse extracellular matrixes(ECM)and stromal cells shapes a condensed physical barrier,which severely hampers the efficient accessibility of nanomedicine to tumor cells,especially these deep-seated in the core of tumor.Such barrier sig-nificantly compromises the antitumor effects of drug-loaded nanomedicine,revealing the remarkable importance of disrupting stro-mal barrier for improved tumor therapy with deep penetration ability.To achieve this goal,various nanoparticle-based strategies have been developed,including direct depleting ECM components via delivering anti-fibrotic agents or targeting stromal cells to suppress ECM expression,dynamic regulation of nanoparticles'physicochemical properties(i.e.,size,surface charge,and morphology),me-chanical force-driven deep penetration,natural/biomimetic self-driven nanomedicine,and transcytosis-inducing nanomedicine.All these nanostrategies were systemically summarized in this review,and the design principles for obtaining admirable nanomedicine were included.With the rapid development of nanotechnology,elaborate design of multifunctional nanomedicine provides new op-portunities for overcoming the critical stromal barriers to maximize the therapeutic index of various therapies,such as chemotherapy,photodynamic therapy,and immunotherapy.