中国化学会第五届全国有机自由基化学会议

双光子吸收(TPA)是同时吸收两个光子实现分子激发的非线性光学效应1，在3D生物成像、三维微加工、光限幅、光动力治疗等领域具备巨大应用价值2-3。

2,2.6,6-四甲基哌啶-N-氧自由基(TEMPO)及其衍生物是醇有氧氧化的经典绿色催化剂，具备选择性好、反应条件温和等优点。但现有TEMPO催化体系仍存在缺陷:均相TEMPO活性组分易流失，难以回收循环;多相TEMPO虽可解决分离回收问题，水相条件下催化效果却不理想。为此，本研究围绕催化剂可循环与水相绿色反应体系构建，设计制备新型非均相离子型TEMPO催化剂，对其催化性能、构效关系及潜在工业化价值开展系统研究。

Chiral azides consttule a versatle class of compounds that are ubiquitous in the specrum of biologicaly active substances. Nevertheless, the inherent high reactivity and elusive nature of azdes have limited the reporting of methods for direct asymmetric azidation of carbon-hydrogen (C-H）bonds. Herein, we present a photoinduced copper-catalyzed enantioselective radical a-C(sp')-H azidation of carbonyl compounds via a 1.5-hydrogen atom transfer strategy. A novel binary bisphosphine and N.N,N-tridentate anionic chiral ligand system functions both as a photosensitizer and a chiral catayst for azidation. DFT studies reveal a remote S.2 mechanism and demonstrate thet the igand evolution strategy combtining ligand modfication and igand self -assembly is critcal for tuning the active chiral space of the catalyst as well as improving the enantioselectivity.

重主族自由基因易二聚分解难以分离，错中心自由基是重要代表。已有Ge(1)自由基阴离子要么无法实体分离，要么依赖二氨基配体、仅低温稳定，烷基取代且电子扰动小的该类物种仍未见报道川。本文实现烷基取代错(1)自由基阴离子的分离表征，其室温热稳定性良好，可开展结构光谱与反应活性研究21。

Achieving precise chemo-, regio-, and stereoselective functionalization of C(sp')-H bonds in inexpensive and readily accessible chemical feedstocks continues to pose a significant challenge in synthetic chemistry. However, while significant efforts have centered on substrates bearinghydridic C(sp')-H bonds, enantioselective radical transformations of abundant feedstocks containing proic C(sp')-H bonds remain underdevelopedIn this work, we report a photoinduced copper-catalyzed enantioselective three-component alkylalkynylation of alkenes with a wide range ofchemical feedstocks, including acetonitrile, ketones, esters, amides, ehers, and amines The reaction employs modified aryl iodides as ydrogeratom transter (HAT) reagents, in which aryl radicals with unable philicity coud selectively abstract either protic or hydridic C(sp')-H bonds based onthe polarity- match effect The resuting carbon-centered radicals then undergo sequential radical addition with alkenes, followed by copper-catalyzedasymmetric C(sp')-C(sp) cross-coupling with terminal alkynes, furnishing various chiral alkynes with excellent chemo-, regio-, andstereoselectivities. This protocol offers a straightforward and mild method to access synthetically valuable chiral molecules directly from widely available chemical feedstocks, highlighting its efficiency and broad applicability.

In photo-induced, radical-mediated carbon-terminus carborane functionalization, criticalconstraints include intricate substrate precursor synthesis, the requirement for ultravioletlight, and costly photosensitizers. This study employs cost-effective and readily availablecopper complexes as photocatalysts, enabling the successful atom transfer radical addition(ATRA) reactions between iodocarboranes and unsaturated bonds. Using this catalyticsystem, a series of structurally unique carborane-containing iodinated compounds and AIE-active molecules have been efficiently constructed.

Herein, we have achieved the one-step synthesis of a series of o-carborane amide derivatives directly from o-carborane carboxylic acids using commercially available triphenylphosphinedibromide as the activating reagent. Mechanistic studies demonstrate that the strong bond-forming tendency and excellent leaving ability of the P-0 bond effectively inhibit both the decarboxylation and the leaving tendency of the o-carborane unit.

Carboranes are an important cass of boron custer compounds with broad applications in medicine, materials science and catalysis. However, the site-selective functionalization of their B-H bonds remain a long-standing challenge owing to the nearly identical chemical environments and high bond dissociation energies (BDEs) of these bonds. Traditional approaches generally rely on precious metal catalysts, harsh reaction conditions, or substrate pre-functionalization, which significantly limit their synthetic utility. Herein, we report the first direct B-H/O-H cross-coupling of o-carboranes with alcohols, enabled by heteroleptic Cul) complexes under mild photocatalytic conditions. This protocol achieves highly regioselective B(4)-H alkoxylation with a broad substrate scope and excellent functional group tolerance providing a facile route to diverse carborane-based building blocks. Mechanistic studies reveal that the benzoyl directing group effectively amplifies the difference in BDEs between B(3)-H and B(4)-H, thereby enabling selective activation of the B(4)-H bond via 1,5-hydrogen atom transfer (HAT). Notably, for the first time, we demonstrated that aboron radical -polar crossover process mediated by the heteroleptic copper catalyst converts boron radicals into highly electrophilic boron cation intermediates, which can be directly trapped by weakly nucleophilic alcohols to form B-0 bonds. This work establishes a new and general strategy for carborane B-H functionalization via radical pathways.

The one step construction of multiple contiguous steroogenic centers to acces structuraly complex, enantioenriched molecules remains a longstanding challenge inorganie synthesis and has gamered considerable atention. Herein, we report a photoinduced copper-catalyzed site- and stercoselective B-C(sp)- H alkyaylation ofycloallyl amines via an intramolecular 1.5-lydrogen atom transfer (HAT) strategy, achieving the desymmerizing radical cross-coupling (DRCC) of enantiotopicC(p)-H bonds to fom C(p')-C(sp) bonds in the challenging unstrained ring system. For a range of acyclic amine substrates, this reaction also cxhibits cxcelentsite-sclectivity This practical protocol displays broad functional group tolerance and delivers cxcellent stercosclectivity via substrate contro, instlling mutiple chiraenters in one step. DFT calulations indicate that the radical alkynylation is achieved through a concerted coupling pathway Structural analysis unveils that the robust-Ht hydrogen bond and the positioning of bulky groups in cquatorial orientations are two key factors that stabilize the concerted coupling transition state and guarantees high enantioselectivity.

a) lIow to achieve a reversible reaction? b) Nickel-clectrocatalytic platform enabling stereosclecrive cross-dchydragenative acyloxylation andreduetive decoupling

The synthesis of drug-like saturated cycloalkanes is morecomplex than theirtwo-dimensional aromatic analogues. Aformidable challenge lies in synthesizing all isomers of multi-substituted cycloalkanes. Here, we have reported a cobalt-catalysed system that enables stereodivergent hydroalkylation ofsubstituted methylenecyclohexanes (MCHs) with exceptionalversatility. Strategic manipulation of ligands facilitates the synthesisof all isomers of di-substituted cyclohexanes, piperidines, andmulti-substituted cyclohexanes.

Radical carbonylation has emerged as a crucial and alternative method for introducingcarbonyl groups with enhanced selectivity and broader substrate compatibility. However,currently, the substrates suitable for these processes are primarily limited to those that canundergo radical induction to form the corresponding monoradicals as key intermediates. Herein,we report a photo catalytic energy transfer-enabled diradical carbonylative cyclization ofbicyclo[1.1.0Jbutanes with CO and commercially abundant alkenes/alkynes to assemble avariety of 4-oxo bicyclo[3.1.1] heptanes and heptenes. The subsequent diversification of theincorporated carbonyl group further allows rapid exploration of structurally varied derivatives.Density functional theory computations reveal that the success of the reaction is determined bythe competition between the desired three-component [2o + 2n + 2a] cyelization pathway andthe [2o + 2x] cyeloaddition and alkene dimerization pathways.

Introduction: The asymmetric contra-thermodynamic double-bond isomerization of intemal alkenes to enantioenriched terminalalkenes remains a formidable challenge, largely because such substrates often lack activating functional groups that can be recognizedby chiral catalysts. Herein, we report a combined photoredox/chromium catalytic system that enables highly asymmetric double-bondisomerization of internal alkenes to enantioenriched terminal alkenes. This work provides an atom -economical, directing -group-free strategy for the asymmetric contra-thermodynamic positional isomerization of alkenes.

The dearomative functionalization of indole derivatives hasgarnered significant research attention, as it provides directaccess to structurally diverse indolines-a privileged class ofscaffoldswidelyfoundandinnaturalproductspharmacologically active molecules. Among the variousderivatives, 2-substituted indolines are of particular importance.Consequently, the development of efficient synthetic routes tothese valuable heterocycles remains a high-priority goal.Currently, well-established indole dearomatization strategiespredominantly rely on the innate nucleophilicity of indoles,exploiting electrophilic attack at the C3-position, followed bynucleophilic trapping of the resulting iminium species.Alternatively,transition-metal-catalyzeddearomatizationprocceds via migratory insertion of the C2-C3 a-bond into ametal-carbon bond, providing a robust route to diverse indolineproducts. While this approach overcomes the intrinsic C3nucleophilicity of indoles by employing an intramolecular tetherto direct regioselectivity, the preinstallation of the tetherintroduces additional synthetic steps.

PCET VS HCET

Strategies for the synthesis of 1,3-alkyl-heteroaryl BCPs

EDA complex-driven synthesis of thioethers from aryl halides, or aryl thianthrenium salts with thiolsa)

Sulfamoyl fuorides have emerged as SuFEx (sufur fuoride exchange) hubs for cick chemistry ligation of bioactive molecular fragments orprecision-controlled polymerization. These fuorinated motifs are generally more aqueous stable than their analogues such as sulfonylfuorides and fuorosufates, and are increasingly recognized as bio privileged substructures in drug and agrochemical discovery. Existingsynthetic routes largely depend on group transter protocols from preformed fuorosufonyl reagents.23 Late-stage labeling with fuorine-18serves to advance clinical care and drug discovery via positron emission tomography (PET). Synthetic methods for [teFsulfamoyl fuoridesare fundamentally based on isotope exchange. None of the method has enabled no-carrier-added (NCA) protocol forradiofluorosufonylation of amines. Herein, we provide nitrogen-centered radical mediated assembling fuorosulfonylation reactions,enablingn ea preoinica evaaton or te esn syntesized ersurAr urprida and sn io ocara peson p agingcollectively highight the potential physiological stability of sulfamoyl [ieF)fuoride groups and the potential application of our radical radiofluorosulfonylation strategy.5

Oxiranes (epoxides) are privileged three-membered oxygen-containing heterocycles in drug discovery and organic synthesis owing to their unique ring strain, rich reactivity, and broad biological relevance. Herein, we present a photoinduced radical approach to oxirane synthesis, enabling the transformation of diverse, readily available feedstocks into structurally diverse epoxides under mild conditions. By harnessing radical reactivity, this platform provides versatle synthetic opportunities for the construction and functionalization of valuable oxirane-containing molecules.

Cyclopropane is a highly strained system (-27.5 kcal/mol) whosereactivity resembles that of C-C double bonds. When donor andacceptor substituents are placed at adjacent positions, its C-C bondscleave more readily, and strain-release-driven ring opening offers broadprospects for developing new synthetic methods. This work focuses onthe ring-opening conversion of cyclopropanes into chain-like systems toaccess a range of 1,3-difunctionalized products. However, such ringopenings typically rely on Lewis acid catalysis, or proceed via metalcatalysis or photooxidative radical cation pathways, suffering fromharsh conditions and difficult selectivity control. Inspired by radicalanion processes, we proposed directly reducing cyclopropanes to radicalanions to enable asymmetric ring-opening coupling. Herein, we report aphotoinduced copper-catalyzed direct reductive opening ofcyclopropanes. This strategy overcomes the reliance of traditional ring-opening modes on Lewis acids or radical cations, and affords a range ofalkynylated products in high yields and high enantioselectivity undermild conditions.

手性碳-碳键的精准构筑是合成化学的难题。尽管过渡金属、酶及有机小分子催化等方向取得了显著进展，但当底物取代基完全由脂肪族碳链构成时，由于缺少显著的电子和立体差异，底物高对映选择性转化仍极具挑战。在本工作我们提出了“伞状手性口袋”分子识别新模式，可精准区分底物中电子和空间结构相似的两个脂肪族取代基，实现了全脂肪族手性碳中心构筑。

Biocompatible and Circular Amide-Bond Formation

Akene hydrophosphonylation constitutes an indispensable tool for the synthesis of alylphosphonates which have found widespread aplications in phammacoutcal, agrochomicals and matarials science, Athough numarous methods for alkone hytrophosphonylation have boen roported, achioving Markovnikoysolectivity wth unactivatad alkons romains a formidable challngo. Horoin wo report the dovclopmont of a nove class of phosphites teaturing a unique N-0- P linkag.namely dialkyl phthallmidy phosphites, which serve as ficient radical trapping reagents, Using dfillyl prthalinidyl phosphites as phosphonylating reagonts anddiphenylslane as the hytrogen donor, he cobattcatalyzed reaction of unacthvated akenes roceeds smoothy at rom temperature, delvering excusvely Markoynikoytydrophosphonylation products in satstactory yields. Notably the transtormaton exhibits excellent functional group tolerance, enabing late stage modifcation of drugdervatives. A mechanism myorving cobalt hydride- medlated ydrogen atom transter, alyl radical addtion to phosphtes, F-scission of phosphoraryl radicals and oxidation of Col to Coll by phthalimidyl radicals, is proposed.

A. Anti-Markovnikov hydrocarboxylation of terminal alkenes with CO2 radical anion

Aliphate carboxylc acids are abundant stable, and cost ofctive, rendering thom ideal substrates for ste-specte C(ep')-P bond formaton via decartoxylatve pathways However, the drect catalytic decartoxylaive phosphonytation of these acids remains a signifcant chalnge. Herein, we repart the development of a noveldlas of phosphites featuring a unique N-0-P tinkage, namely dfilyl inidy phosphites, which serve as fficien radical traping reagent. These reagents enable theton-cata yzed dercarboxylative phosphonylation of alphatc carboylc acids to proced smoothly at raom temperature under vstble lght irediation The transformationccommmadates prmary, secondany, and tertiary llyl acids, delivering the corasponding allylphosphonates in satistactary yelds with broad functional group tcleranceA rea ction mechaniam ivong igand-to-metal charge transtor LMCT) tom feric carboxy ate., -sctsstion of phosphoranyl radtcal nternediates leading to N-0 bond cleavage and single electron oxidation of ferrous ions by imidyl radicals, is proposed.

The direct functionalization of alkyne triple bonds using a radical strategy providesan efficient platform for creating a wide range of substituted alkenes. However,developing a multicomponent enantioselective radical reaction using feedstock alkynes toforge all-carbon quaternary stereocenters-while addressing challenges related tocompatibility, selectivity, and efficiency-remains relatively rare. Here we report anenantioselective electrochemical nickel-catalyzed three-component cross-coupling ofreadily available terminal alkynes, diverse racemic alkyl radical precursors, and grouptransfer reagents (such as (TMS),Si-H, RSe-SeR, RTe-TeR, and CHI,), achievingexcellent regio-, stereo-, and enantioselectivities (more than 70 examples, up to 95% ee).Electricity-mediated difunctionalizations significantly expand the scope of both aliphaticand aromatic alkynes, demonstrating excellent functional group compatibility. The key tosuccess lies in the rational design of anodically generated nickel-bound tertiary radicalintermediates, which stereoselectively capture alkynes to form vinyl radicals andparticipate in subsequently diverse group transfer processes to enable the intermolecularand anti-stereoselective di-functionalization of alkynes. This approach allows thetransformation of terminal alkynes into diverse structural entities with a-quaternarystereogenic centers.

The selective transformations of organometallic reagents are central to moder synthetic chemistry. The higher stability of the C-Si bond compared to the C-B and C-Mg bonds. While this stability makesorganosilicon reagents easier to handle and more storage-friendly, i also restricts their reactivity in certaintransformations (Figure 1a). Traditionally, C-Si bond functionalization has relied on two-electron processesThese methods are generally limited to activated C-Si bonds, and often require Lewis base or Lewis acidto facilitate the reaction (Figure 1b). Currently, photocatalytic methods mainly enable the cleavage andtransformation of activated C(sp3)-Si bonds, while the cleavage of strong C(sp3)-Si bonds remainschallenging. we envisioned that photocatalytically generated hydroxyl radicals might be able to attack theintermolecular unactivated C(sp3)-Si bonds, enabling the production of alkyl radicals that could be functionalized (Figure 1c).

270 experiments out of 222,768 possible conditions High site selectivity and broad substrate scope

Functional group interconversion (FGD) is central to organic synthesis, enabling moleculardiversification and access to high-value compounds from abundant, inexpensive feedstocks.Converting amino groups into other functionalities has drawn special attention because aminesare structurally rich and naturally abundant. Beyond the two-step Katritzky-salt / photoinduceddeamination route, direct deaminative functionalization via molecular editing has recentlyflourished, delivering halogenation, hydrogenation, alkylation and trifluoromethylation yet this paradigm remains in its infancy.

不对称自由基催化

自由基催化

Concept of free organic radical catalysisl23l

相比于红光和绿光材料，蓝光材料因具有较大的能带间隙，普遍存在发光效率低、寿命较短等问题。目前，商业化蓝光材料多为稳定性较高的传统荧光材料，其受自旋统计限制，激子利用率最高仅为25%；而磷光和热活化延迟荧光材料虽可提高激子利用率至100%，却常因激子寿命较长而容易引发效率滚降与器件老化。开壳层有机自由基的基态与激发态均为双线态，可避免自旋禁阻，不仅可以再理论上实现100%激子利用，还具有纳秒级激发态寿命，为兼顾蓝光OLED的效率与稳定性提供了新的材料设计路径。

过渡金属催化的对映选择性C(sp)H键官能团化反应一直是不对称催化领域中的长期排战。基于氧化型氯原子转移(HAT)的交又信联策略，通过使用易制备的和和环丙统醇四作为烷基化试剂，与简单易得的含氧杂环化合物，能够在温和条件下实现操催化对映选择性C(sp)H键院基化反应。该策略使用过氧化物同时作为氧化剂和氢原子转移试剂，展现出卓越的原子和步骤经济性。此外，该方法可应用于天然产物及药物分子的后期修饰，以及多种手性砌块和药物中间体的合成。

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The deyclopmen of a catalytie actiyation mode enables the innoyation of synthctie mcthods toward functional moleeules Receny radical NHC catalysts has attracted onsiderble aenion and achieyed remarable sucess. I unlocks the Potential to activate inert substales and access valuable ketones tat are beyond the reah ofonyentional methods. Howeye, this strategy has so fa been limited to the actiyation of carthonyl compoud fo kctone syuthesis. In conirast the radical actiyation of ininesinder NHC catalysis for faclle syathesis remais an umet challenge. Herein, we repor the NHC-catalyzed single electon oxidation and lylation of inines. Varous agentsincluding Tognl reagen a-iododif uoroacetate, phenyldifuoroiodomethy )sufione, perfuoroallyl fodide, and peroyester, royed to be effetiye single-electon oxidantsThis versatliy enabled the developmen of bth an alkene difunctionalization and a dchydrogenative coupling reaction. Prelininary mechanistie studies suppor the proposed Teaction patiway. The utliy of this method is demonstrated through the late stage functionalization of pesticide-related molecules and the divergent transfomation of the oroducts.

Background: Applications of bioisosteres in medicinal chemistry

硫羰基加成-开环自由基共聚为合成可降解乙烯基共聚物提供了一种通用策略。然而高活性硫羰基内酯 单体种类有限，并且缺乏同时与多种乙烯基单体进行高效共聚的能力。藉此我们发展了一种BINOL衍生的 硫羰基内酯，联蔡骨架可同时影响硫羰基的电子结构、开环后自由基中间体的稳定性，以及由环张力释放 所提供的开环驱动力。该单体对乙烯基单体表现出良好的共聚兼容性，可近似实现交替共聚(M1=0.10，rM2 -0.40)，并在RAFT聚合条件下得到高达83%硫酯结构单元的共聚物。结合实验与理论计算，进一步揭示了 联蔡骨架对共聚反应的调控机制。此外，刚性的阻转异构骨架能够在自由基共聚过程中保持轴手性，从而 为制备可降解手性聚合物及水溶性手性纳米粒子提供新的途径。通过双功能硫羰基内酯单体的设计与合成， 为后续开发高性能芳香硫羰基内酯、拓展可降解乙烯基聚合物的结构与功能多样性提供了依据。

Selective allkyne semi-deuteration requires control of Z/E selectivity. D incorporation and overeduction. CoBr /dtbpy electrocatalysis uses D20and AcOD to afford deuterated Z-alkenes under air at room temperature.

Introduction : We report a triazene-carbene hydrogen atom transfer (HAT) catalyst platform that, in combination with hexafluoroisopropanol (HFIP), preferentially functionalizes non-activated alkane C-H bonds in the presence of heteroatom-containing substrates. Mechanistic studies indicate that this selectivity arises from the combined effect of the pocket -like HAT catalyst and hydrogen-bonding interactions between HFIP and the heteroatom-containing substrate, which electronically deactivate the proximal a-heteroatom C-H bonds and thereby allow kinetic control to override the intrinsic BDE ordering.

1. Fluoroalkyl-containing drug molecules

Oxa- and azabicyclic alkanes are valuable three-dimensionalscaffolds in drugs and natural products. However, strain-driven ringopening makes their ring-retentive asymmetric functionalizationchallenging. We developed a cobalt-catalyzed enantioselectivehydroalkylation of bicyclo[2.2.1]alkenes, enabling the highlyenantioselective construction of tertiary carbon stereocenters withinoxa- and azabicyclic frameworks. Noncovalent catalyst-substrateinteractions govern stereoselectivity, and the method enables late-stage modification of bioactive molecules and the synthesis ofpotent fungicidal agents.

合成电化学被IUPAC列为2023年度化学领域十大新兴技术之一。该技术以可再生电能为驱动力，摒弃了当量氧化还原试剂，具有绿色安全、可调可控、条件温和等显著优势，被公认为绿色合成的有力手段。在“双碳”目标与绿色低碳转型背景下，合成电化学正展现出突出价值:既能降低资源消耗与环境负担，又能赋能高端精细化学品制造升级，推动传统化工向高效、清洁、可持续方向变革，助力构建绿色低碳新工业体系。

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1. Boryl radical enabled a three-step sequence to assemble all-carbon quaternary centers from CCl, groups

The selective fnctionlization of ycloprpylnines Ias bong remained halenging due to hei iniced tectronic bias ad the dificuly of achiering ficien bond polarization Iere, we report aoppe-cata yzed tlorcoanid- directed stratey that enables 1.3-dfinctionalization of eyckopropylanides in a Single stp. This nethod leyeragestai- driven single- eleton reduction to generaitgn coned audicals, which undergo rapid -ssion to proice gsatie raudical mermetates that can be cicieonly grugped by a proad ang of nucleophiles the aproah providsJular aeces to a,difnctiondlized anines fom simple preusor, fature broad ubstratescope including atstage dirersification of dnug deriatives such as mexiletin and edecoxib, anddimnaes the reed for strong oxdants. By combining raudical reativity with a direting gop stratcey this alon-econoncal protocol cstablshes a general pltform for conitnucdin mod pharmaceutically relevant amine architectures and opens eficient opportunities in synthetic and medicinal chemistry.

hnenids n prlegel neural motiS in plamaenrick, naura rodaets, and nheti memediates oyet genern ind module methnt ior aeesihg hihy uncinalied lylie mnanids remin inial Necem we repor s sopper etalysd ing-ping fincionalatin of rally aalihle N -thioogyelopopytanids wih dingse muckephils poving eficin aces to rnad ange of intionalid ) enanids Undet mld h d Sndl E aa het MR te e Dh S d Rdnemelies ue regpled y opper pwis uiuaey dieri syluied pophoyluied eyoy, yloy and thip-subslaue panis with 201 2-letivty Can scale sntheis and dnese doyst an complex enamide scaffolds.

揭经催化双官能团化是构筑复杂分子骨架的重要合成策略，然而，在烯烃碳 碳双键上选择性构建两个不同院基一烷基键仍存在很大挑战。现有方法多依教导向基团或复杂自由基前体，烯烃的区域对映选择性双院基化难以实现，目尚无对映选择性获取两种区域异构体的合成方案。本文发展光氧化还原/银协同催化的区域可切模对映选择性地短三组分双院基化反应，可模块化制备光学纯天然及非天然p-7氨基酯核心骨架。该反应以非活化烷基卤代物与质子型C(p)日键为偶联底物，底物普适性良好，区域与对映选择性优异，反应借助卤原子转移(XA)中烷基碘、溴产生自由基的速率差异实现区域发散调控，并可用于药物相关手性分子合成，展现出良好的合成应用价值。

Radical ring-opening polymerization (rROP)of vinyleyclopropanes (VCPs)affords polymers with low volume shrinkage but often limited ductility. Here, two radical-based strategies were explored to une their properties. First, an NHPI-functionalized VCP monomer was polymerizedvia controlled rROP under visible-light irradiation,and the resulting polymer underwent photocatalytic reductive decarboxylation followed byhydrogen atom transfer. This post-modification transformed a glassy, britle polymer into a sof, ductile material, with a tensile strength (og)of1.47 MPa and an clongation at break (eg)of 131%. Second. preliminary EtVCP/Se copolymerization results showed decrcasing glass transitionemperature with increasing sulfur feed. The copolymer prepared at an EVCP/S feed ratio of 100:2 exhibited a yield stress (a,) of 2.89 MPa and εB of 436%.

聚多胺在基因递送、催化和能源材料等领域具有广泛应用，其性能高度依赖主链氮原子的排布，而传统开环聚合主要获得C2NI、C3N/型聚多胺，结构拓展受限。针对上述不足，我们发展了钯催化的质子转移烯丙基胺化聚合，实现了高区域选择性C2N1与C4NI型聚多胺的合成，但竞争性的两性离子聚合导致分子量难以精准调控。因此我们将质子转移烯丙基胺化聚合体系进一步拓展，以苯并乙烯基恶嗪酮为单体，在中性条件下实现全新CSN1型聚多胺的可控合成，可高效制备结构明确的新型聚多胺及其共聚物。

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Highlights: The development of carbon radical catalysis bridges the gap of carbon radical chemistry.

Model reaction and development of primary photoenzyme library

Abstract: Molecular editing seeks to reshape existing molecular architectures through selective bond reorganization. We have developed a general amino-migration paradigm in which 1,2-amino translocation serves as a programmable radical relay connecting functional group repositioning with downstream bond formation. This concept has been realized across photoredox, MHAT, and interrupted Sn2 catalytic manifolds, enabling the synthesis of diverse p-amino acids, alkylamines. Collectively, these studies establish amino migration as a general strategy for transforming the amino group from a static functional handle into a dynamic element for molecular reconstruction, opening new opportunities for synthetic strategy development, scaffold diversification, and molecular complexity generation. Our group is also pursuing further studies on amino migration and its synthetic applications.

Photochemical rearangements via diradical intermediates have emerged as a transformative paradigm in moder organic synthesis, offeringunparalleled control over molecular architecture through radical-based skeletal remodeling. We recenty developed several examples to accessstrained architectures through di--ethane rearrangement and , o-Methane rearangement strategies. In this presentation, I wil highight ourecent efforts toward pholochemical diradical rearrangement enabled by energy transfer catalysis. The first part wil focus on the development of ring expansion. 56 The second part wll discuss the unexpected chemoselectivity in radical ary translocation via photosensitization.

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Design of biomimetic synergistic asymmetric catalysis.

Examples of electrocarboxylation scenarios.

Partially halogenated alkyl motifs occur in bioactive molecules. Selective,stepwise C-X activation remains challenging across C-F, C-CI and C-Brbonds.

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当前工业上对二氧化硫进行回收利用的途径主要为将其转化为单质硫或硫酸，但经济价值相对较低。将二氧化硫转化为有价值的有机硫化合物能够为减排和资源利用提供可持续的解决方案。作为一类有机合成与功能材料的前体，亚硫酸酯在工业上通常需要采用二氯亚砜作为原料进行生产，具有相对较高的毒性和污染性，在此我们开发了一种配对电解策略，能够在温和条件下直接将二氧化硫转化为环状亚硫酸酯。

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Abstract: Precise regulation of the coordination environment in iron -based single-site catalysts (Fe SSCs) is essential for promoting thetwo-electron oxyger Teduction reaction (2e ORR) toward efficient hydrogen peroxide production. However, the atomic-scalerelationship betwen coordination structure and reactiorpathway remains insulficienly understood.In this work, a series of ironmolecular catalysts with unable axial coordination wererationally designed to systematicalyinvestigate how ligand-mediatedregulation of the metal site and ligand conjugation dircct the 2e ORR pathway. Combined elecrochemical measurments, insituspectroscopic analysis, and theoretical calculations demonstate that electron-rich Fe centers weaken OOH adsopion, therebyenhancing H,02 selectiviy Incontras, increased ligand conjugation modifies the local catalytic microenvirommen, strengthensoxygon intermediate adsoption, and reduces H,O, sclectivity. Ainear stcthir acirviy relationshin betren the Rrt radornotenial and H. selectiviy s stab ihed idenrising this rodo potenial as a refiable desgiorFaradaic effcieney and an H,O, yicld of 72.9 mol 1h1at 400 mA cm2. These findings provide mechanisic insights fordesigning highly sclective 2e ORR electrocatalysts via coordination engineering.

Abstract: Direct C-N bond formation from nitroarenes offers an appealing alternative to conventional routes that rely on aniine intermediates, yet existing metal catalyzed approaches often suffer from narow substrate scope and the need for stoichiometric additives.Herein, we report a paired electrolysis strategy that enables highy selective para-C-H amination of phenols with nitroarenes, deliveringunprotected p-hydroxy diphenylamines in a single step without transition-metal catalysts or extemal reductants. Central to this advance is amultifunctional automated injection electrochemical mas spectrometry (AIEC-MS) platform, which accelerates reaction screening, identifesproductive electrochemical conditions, and reveals broad compatibility with diversephenolic and nitroarene substrates. Real-time EC-MSanalysis captures key transient intermediates-including a putative ary-nitrene species -thus providing mechanistic visualization that clarifesnow anodic and cathodic events cooperatively generate the reactive partners. Together, these insights demonstrate both the synthetic utlty and mechanistic distinctiveness of paired electrolysis for direct C-N bond construction.

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Electrooxidation strategies for synthesizing easily oxidizableproducts encounter significant challenges, particularly whenproduct oxidation potentials are lower than those of reactants orhigh current densities are required. Electrooxidative synthesis oftrivalent organophosphorus compounds (OPCs III) from whitephosphorus (P4) is promising but limited by over-oxidation andpoor selectivity. Here, we present a tandem electro-thermalpathway to overcome these issues. The method firstelectrooxidizes P4 to form a stable trivalent phosphorus transferreagent, which is then thermally converted into various high-value OPCs III. Using hexafluoroisopropanol (HFIP) as thenucleophile and optimizing a tetrabutylammonium iodide (TBAl)-4-dimethylaminopyridine (DMAP) adduct catalyst, we efficientlypreparedelectrophilicphosphorusreagentviaanelectrosynthesis.The adduct promotes P4 oxidation andstrengthens HFIP nucleophilicity, enhancing electrooxidationperformance. This strategy enables high current density,hundred-gram scale synthesis without yield loss, and toleranceto intermittent green electricity.

Periodic polarity reversal enables alternating oxidation and reductionevents. Programmable waveforms regulate electrochemical reactivity. Unsymmetrical Alternating current (AC) maintains high Cu(Il) intermediate concentrations under dynamic conditions. Waveform modulation enables diverse Cu-catalyzed C(sp3)-Hfunctionalizations. Unlocking the potential of AC-driven transition-metal catalysis.

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Aminoarenes are important molecules for broad applications in nearly all modernindustries that involve chemicals. Direct and site-selective C-H bond amination ofarenes provides the most efficient and convenient method to prepare aminoarenes. Amain challenge is to selectively install the amino group (or other functional groups) tothe distal para-carbon of arenes (especially multi-substituted arenes) during the C-Hbond functionalization events. Herein, we address this problem by designing a newstrategy via a sequential radical dearomatization/radical amination/rearomatizationprocess for para-selective amination of benzyl alcohols. The para-selectivity of ourreaction is completely independent of the electronic and steric properties of the othersubstituents of the arene substrates. Aminoarenes with many substituents (up to fullsubstitution) and diverse substitution patterns, including those difficult to synthesizepreviously, could be readily prepared using our protocols. Further exploration of thecurrent strategy shall lead to other challenging C-H functionalization of arenes.

Catalytic stereodivergent synthesis, which accesses thefull complement of stereoisomers from a common precursor set, is aparamount objective in drug discovery. However, achieving thiscontrol via radical-involved pathways remains a formidable frontierdue to the transient nature of open-shell intermediates. Here, we reporta unified chromium-catalyzed platform that harnesses a radical-polarmechanism to achieve the fully ligand-controlledcrossoverstereodivergent synthesis of chiral B-fluoro alcohols. We demonstratethat the stereochemical outcome is not inherent to the substrate but isdictated by the ancillary ligand through distinct non-covalentinteractions: a chiral bisoxazoline ligand enforces a rigid transitionstate via fluorine-mediated hydrogen bonding to selectively deliversyn-diastereomers, whereas a chemically distinct pyridine-imidazolineligand exploits electronic desymmetrization via n-n stacking to invertselectivity toward anti-isomers. Notably, this protocol enables theprogrammable assembly of all four stereoisomers of fluorosugarderivatives.

Abstract: Copper-catalyzed enantioconvergent radical alkylation of oxygen and nitrogen nucleophiles is an efficient asymmetric strategy. It generally proceeds via inner-sphere radical capture/reductive elimination or outer-sphere Sn2. Herein, a rebound-S,2 mechanism is put an forward for the transformation of radicals with an anchoring group. A dangling radical center chelates Cu(Il), intramolecular radical capture by copper(ll), nucleophile dissociation, and S,2 then give the stereoinversed product. This avoids fused-ring strain, outcompeting reductive elimination. The computational study indicate enantioselectivity is governed by classical S,2/rebound-S,2 competition. Quantitative steric-electronic effects dissection (QSED) quantified radical-catalyst interactions influencing mechanism competition. The ligand-radical dihedral angle e predicts S,2 vs rebound-S2 discrimination. The smaller 0 (S 64.0%) in the phenoxy copper(ll) amide intermediate makes rebound-S,2 kinetically favorable, while a larger 0 increases the steric demand for transition state formation, particularly for the radical capture transition state

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Partially halogenated alkyl motifs occur in bioactive molecules. Selective,stepwise C-X activation remains challenging across C-F, C-CI and C-Br bonds.

Precious-metal-free photocyclization provides three distinct cyclic frameworks by tuning the N-substituent.

In contrast to the Michael addition that utilizes nucleopliles, the conjugate addition of electophiles to electon-deficient alkenes is polanity-nismatched and thus a long -standing chllenge in syathetic chenistry. By using tertiary phosphine as a general and mild umpolung mediator for C-Cdouble bond, a visible-light plotocatalytic conjugate acylation with acid anlydrides is accomplished. Mechanistic studies indicate a novel phosphineradical cation -mediated umpolng of alkenes. followed by a polar acylation, thus offering a good solution to overcome the incompatibility of acidanlydrides under the traditional two- or one-electron umpolung reaction conditions. The radical-polar crossover umpolng strategy disclosed hereinwill unlock broader chemical space for alkene fiunctionalization by establishing a new retrosyuthetie logic for assembling C-C bonds.

We have developed a novel strategy for synthesizingdisilyl-substituted allenes and bis(silyl)propenes usingpropargyl and allyl gem-dichlorides with chlorosilanes inthe presence of magnesium. This approach achievesgood to excellent yields without requiring transitionmetal catalysts or ligands, highlighting its efficiency andinnovation. Preliminary mechanistic studies show thatdichlorides react with magnesium to generate carbonnucleophiles, which undergo S,2 substitution withchlorosilanes to form the final products. This methodoffers a straightforward synthetic route with potentialapplications in organic synthesis.

1.This work: remote spin-center shift through an aryl ring for deoxygenation and deamination

N-Fluoroalkyl groups are valuable motifs in medicinal chemistry. Carbonimidic difluorides(R-N=CF2) are key intermediates, but conventional access often requires prefunctionalizedamines, excess fluoride or harsh conditions, limiting product diversity. Objective: use a bench-stable precursor to generate difluoromethylenimino radicals under visible light and control subsequent transformations of R-N=CF2.

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Photocatalysis is primarily initiated with ultraviolet/blue light, which has several drawbacks, namely,deficiencies in reaction efficiency and scalability. Designing catalysts that can absorb low-energylight offers a promising solution aiming at these drawbacks.1 Building on our previous work oncluster-based photocatalysts, 2-3 we evaluated the deep-red photocatalysis of Au1s(DPPOE)(SR),nanocluster catalyst (where DPPOE = bis(2-diphenylphosphinophenyl)ether and SR = 2,4-dichlorobenzenethiol).4 The nonlinear optics (i.e., the two-photon absorption) of the Au1snanocluster was determined, which acted as the prerequisite for its application in two-photon fslaser photocatalysis. The Aus nanocluster exhibited exceptional photocatalytic performance indeep-red LED light-driven Povarov-type reactions via a single-photon process, leading to thesynthesis of complex tricyclic N-heterocyclic compounds derived from bioactive molecules. Ourinvestigation into the reaction mechanism provided compelling evidence that the photocatalysisproceeds via a radical pathway, with superoxide radicals playing a crucial role in the reaction.Additionally, the scalability of the photoreaction and the exploration of other deep-red light-induced reactions have underscored the versatility and the broad applicability of the Au1s photocatalyst.

Nitrogen-containingbicyclicscaffoldshaveattractedconsiderable attention in medicinal chemistry and drugdiscovery owing to their structural rigidity and potential to serveas versatile molecular frameworks. In particular, relateddiazabicyclo[3.1.0]hexane derivatives have been investigated fortheir biological activities, highlighting the interest in this class ofnitrogen-containing architectures. Meanwhile, visible-light-induced transformations of diazo compounds have emerged asversatile strategies for generating reactive intermediates andconstructing structurally complex molecules under mildconditions. Recent studies on the photochemical reactions ofvinyldiazo compounds with diazo reagents have proposed 2,3-diazabicyclo[3.1.0]hex-2-eneskeyintermediates inassubsequent skeletal rearrangements. Herein, we report a blue-light-induced coupling of vinyldiazo compounds withdiaryldiazomethanes, providing access to a diverse range ofisolable substituted 2,3-diazabicyclo[3.1.0]hex-2-enes.

Phenanthridines are valuable in optoelectronic materials, TADF emitters, DNA probes, and bioimaging, but their construction often relies on isocyanides, prefunctionalized substrates, noble-metal catalysts, high temperatures, or strong Lewis acids. Herein, we report a metal-free and mild one-pot strategy using unprotected 2-arylanilines as dinucleophiles and a-diazosulfonium salts as dielectrophilic carbon-insertion reagents.Consecutive nucleophilic attacks followed by blue-light/O2-mediated oxidative aromatization afford phenanthridine derivatives.