UV-to-NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation

Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR-absorbing upconversion nanoparticles (UCNP) with UV-Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C−C coupling to fabricate a UC−POP nanocomposite. The light-harvesting ability of UC−POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC−POP. A three-times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC−POP, subsequently boosting the photocatalytic activity of UC−POP−Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC−POP−Au compared to POP and UC−POP due to the facile electron-hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting.     

Porous Organic Phenanthroline-Based Polymer as an Efficient Transition-Metal-Free Heterogeneous Catalyst for Direct Aromatic C−H Activation

Direct C−H bond transformation has been regarded as one of the most important areas in organic synthesis in both academia and industry. However, the heterogeneous transition-metal-free catalysis of direct C−H bond transformation has remained a contemporary challenge. To tackle this challenge, we designed and constructed a porous phenanthroline-based polymer (namely POP-Phen) via free radical polymerization of vinyl-functionalized phenanthroline monomers. POP-Phen shows excellent catalytic performances in transition-metal-free catalyzed C−H arylation, even better than those of the corresponding homogeneous catalyst, which is mainly attributed to the high density of catalytically active sites in the heterogeneous catalyst. Kinetic isotope experiments and spectral characterizations demonstrate the electron-transfer between the heterogeneous catalyst and the base (t-BuOK), a key step for C−H activation. We believe that this porous organic phenanthroline polymer could open a new door for the design of novel heterogeneous transition-metal-free catalysts for direct C−H activation.     

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation

Three porous organic polymers (POPs) containing H, COOMe, and COO^? groups at 2,6‐bis(1,2,3‐triazol‐4‐yl)pyridyl (BTP) units (i.e., POP‐1, POP‐2, and POP‐3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP‐1, whereas uniform‐ and dual‐distributed palladium NPs are located on the external surface of POP‐2 and POP‐3, respectively. The presence of carboxylate groups not only endows POP‐3 an outstanding dispersibility in H₂O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials.     

Green,General and Low-cost Synthesis of Porous Organic Polymers in Sub-kilogram Scale for Catalysis and CO2 Capture

Porous organic polymers (POPs) with high porosity and tunable functionalities have been widely studied for use in gas separation, catalysis, energy conversion and energy storage. However, the high cost of organic monomers, and the use of toxic solvents and high temperatures during synthesis pose obstacles for large-scale production. Herein, we report the synthesis of imine and aminal-linked POPs using inexpensive diamine and dialdehyde monomers in green solvents. Theoretical calculations and control experiments show that using meta-diamines is crucial for forming aminal linkages and branching porous networks from [2+2] polycondensation reactions. The method demonstrates good generality in that 6 POPs were successfully synthesized from different monomers. Additionally, we scaled up the synthesis in ethanol at room temperature, resulting in the production of POPs in sub-kilogram quantities at a relatively low cost. Proof-of-concept studies demonstrate that the POPs can be used as high-performance sorbents for CO₂ separation and as porous substrates for efficient heterogeneous catalysis. This method provides an environmentally friendly and cost-effective approach for large-scale synthesis of various POPs.     

Embedding Hydrogen Atom Transfer Moieties in Covalent Organic Frameworks for Efficient Photocatalytic C−H Functionalization

Covalent organic frameworks (COFs) have emerged as efficient heterogeneous photocatalysts for a wide range of relatively simple organic reactions, whereas their application in complex organic transformations, like site-selective functionalization of unactivated C−H bonds, is underexplored, which can be mainly attributed to the lack of highly active organophotocatalytic cores. Herein through bonding oxygen atoms at the N-terminus of quinolines in nonsubstituted quinoline-linked COFs (NQ−COFs), we successfully realized the embedding of active hydrogen atom transfer (HAT) moieties into the skeleton of COFs. This novel designed COF (NQ−COF_E5−O), serving as both an excellent photosensitizer and HAT catalyst, exhibited much higher efficiency in C−H functionalization than the corresponding NQ−COF_E5. Specially, we evaluated the photocatalytic performance of NQ−COF_E5−O on ten different substrates, including quinolines, benzothiazole, and benzoxazole, all of which were transferred to desired products in moderate to high yields (up to 93 %). Furthermore, the as-synthesized NQ−COF_E5−O displayed excellent photostability and could be reused with negligible loss of activity for five catalytic cycles.     

光催化有机物偶联/芳构化放氢反应研究进展

光催化氧化还原反应具有绿色、高效、安全等优势,已经在有机化学中得到广泛关注.介绍了基于光催化的偶联/芳构化放氢反应,通过使用光催化剂/催化剂的双催化体系,可用于光催化有机碳-碳和碳-杂原子成键反应,且反应中氢气是唯一的副产物.强调了有机光氧化还原体系的构建与催化机理.     

The Fascinating Chemistry of α-Haloamides

The aim of this review is to highlight the rich chemistry of α-haloamides originally mainly used to discover new C−N, C−O and C−S bond forming reactions, and later widely employed in C−C cross-coupling reactions with C(sp³), C(sp²) and C(sp) coupling partners. Radical-mediated transformations of α-haloamides bearing a suitable located unsaturated bond has proven to be a straightforward alternative to access diverse cyclic compounds by means of either radical initiators, transition metal redox catalysis or visible light photoredox catalysis. On the other hand, cycloadditions with α-halohydroxamate-based azaoxyallyl cations have garnered significant attention. Moreover, in view of the important role in life and materials science of difluoroalkylated compounds, a wide range of catalysts has been developed for the efficient incorporation of difluoroacetamido moieties into activated as well as unactivated substrates.     

Porous Organic Polymers Containing a Sulfur Skeleton for Visible Light Degradation of Organic Dyes

Three novel chemically stable porous organic polymers (POPs) were synthesized by the hydrothermal method; the POPs contain sulfone bonds (TpSD), no sulfur atoms (TpMD), or thioether bonds (TpTD). The catalytic mechanism of the POP with sulfone bonds was studied, and it was found that the wide visible light absorption range, high specific surface area, and the hydrophilicity of the material significantly promoted the catalytic efficiency of TpSD. The presence of O=S=O gives TpSD a higher degree of conjugation than TpMD and TpTD, so TpSD shows the strongest UV/Visible absorption and faster transmission of electrons. The photocatalytic degradation of Rhodamine B (RhB) molecules is approximately 100 % with TpSD and its pseudo‐first‐order rate constant is 0.0770 min^?1, which is the highest among all reported non‐metallic photocatalysts. Moreover, it is also the first time that sulfur‐containing polymer have been used in photocatalytic degradation of dyes.     

NHC Effects on Reduction Dynamics in Iron-Catalyzed Organic Transformations**

The high abundance, low toxicity and rich redox chemistry of iron has resulted in a surge of iron-catalyzed organic transformations over the last two decades. Within this area, N-heterocyclic carbene (NHC) ligands have been widely utilized to achieve high yields across reactions including cross-coupling and C−H alkylation, amongst others. Central to the development of iron-NHC catalytic methods is the understanding of iron speciation and the propensity of these species to undergo reduction events, as low-valent iron species can be advantageous or undesirable from one system to the next. This study highlights the importance of the identity of the NHC on iron speciation upon reaction with EtMgBr, where reactions with SIMes and IMes NHCs were shown to undergo β-hydride elimination more readily than those with SIPr and IPr NHCs. This insight is vital to developing new iron-NHC catalyzed transformations as understanding how to control this reduction by simply changing the NHC is central to improving the reactivity in iron-NHC catalysis.     

Cross- and Multi-Coupling Reactions Using Monofluoroalkanes

Carbon-fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C−F bonds can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C−C bond formation at monofluorinated sp³-hybridized carbons via C−F bond cleavage, including cross-coupling and multi-component coupling reactions. The C−F bond cleavage mechanisms on the sp³-hybridized carbon centers can be primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or carbon nucleophiles supported by the activation of C−F bonds by coordination of Lewis acids; and the cleavage of C−F bonds via a single electron transfer. The characteristic features of alkyl fluorides, in comparison with other (pseudo)halides as promising electrophilic coupling counterparts, are also discussed.     

Directing Group-Promoted Inert C−O Bond Activation Using Versatile Boronic Acid as a Coupling Agent

A simple Ni(cod)₂ and carbene mediated strategy facilitates the efficient catalytic cross-coupling of methoxyarenes with a variety of organoboron reagents. Directing groups facilitate the activation of inert C−O bonds in under-utilized aryl methyl ethers enabling their adaptation for C−C cross-coupling reactions as less toxic surrogates to the ubiquitous haloarenes. The method reported enables C−C cross-coupling with readily available and economical arylboronic acid reagents, which is unprecedented, and compares well with other organoboron reagents with similarly high reactivity. Extension to directing group assisted chemo-selective C−O bond cleavage, and further application towards the synthesis of novel bifunctionalized biaryls is reported. Key to the success of this protocol is the use of directing groups proximal to the reaction center to facilitate the activation of the inert C−OMe bond.     

The Construction of Molecular Complexity from Functionalized Alkylidenecyclopropanes (FACPs)

As a special family of cyclopropanes, alkylidenecyclopropanes (ACPs), exhibit outstanding physical and chemical activities, which provide opportunities to participate in fascinating chemical transformations to access cyclopropane-containing units without ring-opening processes and other unavailable compounds through conventional routes with ring-opening processes owing to their strain-driven reactivity and synthetic accessibility. Nowadays, intramolecular reactions of methylenecyclopropanes (MCPs) or ACPs with adjacent functionalities have emerged as a powerful synthetic protocol for the construction of a variety of polycyclic and heterocyclic compounds with different sized skeletons through catalytic methods. Recently, we put forward the concept of functional alkylidenecyclopropanes (FACPs) and in this Minireview, we will summarize the reactions of FACPs after 2016 including several important early works from three aspects: 1) reactions with distal C−C bond cleavage, 2) reactions with proximal C−C bond cleavage (including ring-expansion reactions), and 3) reactions without C−C bond cleavage.     

Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Transition metal catalysed C−H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C−C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C−H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C−H/C−X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C−H/C−H cross-coupling protocols driven by the activation of monomers’ C(sp²)−H bonds. Furthermore, poly(annulation) via C−H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C−H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C−H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C−H activation polymerization to prepare conjugated polymers were discussed and commented.     

Pd-catalyzed cross-coupling reactions of alkyl halides

Cross-coupling reactions have become indispensable tools for creating carbon-carbon (or heteroatom) bonds in organic synthesis. Like in other important transition metal catalyzed reactions, such as metathesis, addition, and polymerization, unsaturated compounds are usually employed as substrates for cross-coupling reactions. However during the past decade, a great deal of effort has been devoted to the use of alkyl halides as saturated compounds in cross-coupling reactions, which has resulted in significant progress in this undeveloped area by introducing new effective ligands. Many useful catalytic systems are now available for synthetic transformations based on C(sp(3))-C(sp(3)), C(sp(3))-C(sp(2)) and C(sp(3))-C(sp) bond formation as complementary methods to conventional C(sp(2))-C(sp(2)), C(sp(2))-C(sp) and C(sp)-C(sp) coupling. This tutorial review summarizes recent advances in cross-coupling reactions of alkyl halides and pseudohalides catalyzed by a palladium complex.     

BINAP嵌入的多孔有机聚合物在多相不对称氢化反应中的作用

手性多孔有机聚合物具有较高的稳定性和催化活性,广泛用于多相不对称催化中.目前研究多集中在合成具有微孔结构的聚合物,而少有具有多种孔道结构(包含介孔和微孔)的聚合物的报道.之前我们报道了乙烯基修饰的BINAP配体,(S)-5,5'-divinyl-BINAP,将其与不同单体共聚后得到了一系列具有不同孔结构的有机聚合物.其负载的Rh基催化剂在苯乙烯不对称氢甲酰化反应中,表现出比均相更高的产物对映体选择性.本文采用不同的溴代步骤,合成了(S)-4,4'-divinyl-BINAP配体.将这两种具有乙烯基官能团的手性配体按相同的摩尔比与二乙烯基苯(DVB)共聚,得到两种不同的有机聚合物.负载[RuCl2(benzene)]2后,分别得到Ru/4-BINAP@POPs和Ru/5-BINAP@POPs-1.采用一锅法合成了催化剂Ru/5-BINAP@POPs-2;以[RuCl2(p-cyme)]2和RuCl3分别合成了Ru/5-BINAP@POPs-3和Ru/5-BINAP@POPs-4催化剂.N2物理吸附结果显示,Ru/4-BINAP@POPs和Ru/5-BINAP@POPs-1催化剂具有相似的孔道结构;而采用一锅法合成的Ru/5-BINAP@POPs-2催化剂的介孔孔径较大.4-BINAP@POPs和5-BINAP@POPs聚合物的13C核磁显示,其均在145,137和128 ppm处有明显的吸收峰,可归结为萘环和苯环上的碳振动峰;在44.0 ppm处的峰归属为亚甲基上的碳振动峰;31P核磁显示,在聚合物中P基本没有被氧化.将所得到的Ru/POPs催化剂应用于乙酰乙酸甲酯的多相不对称加氢反应中,Ru/5-BINAP@POPs-1催化剂具有与Ru/4-BINAP@POPs更快的反应速率.在相同反应条件下,催化剂活性大小为Ru/5-BINAP@POPs-1>Ru/5-BINAP@POPs-3>Ru/5-BINAP@POPs-4>Ru/5-BINAP@POPs-2.另外Ru/5-BINAP@POPs-1催化剂对β-酮酸酯有着较好的底物适应性,且在釜式反应中可循环使用6次而活性基本不变.分析发现,使用前后的催化剂均没有明显的Ru–Ru键的存在.表明Ru金属高度分散于催化剂上,且具有较高的稳定性,金属不易聚集,这也是其具有高活性和稳定性的原因.     

Cascade Cross-Coupling of Dienes: Photoredox and Nickel Dual Catalysis

Chemical transformations based on cascade reactions have the potential to simplify the preparation of diverse and architecturally complex molecules dramatically. Herein, we disclose an unprecedented and efficient method for the cross-coupling of radical precursors, dienes, and electrophilic coupling partners via a photoredox- and nickel-enabled cascade cross-coupling process. The cascade reaction furnishes a diverse array of saturated carbo- and heterocyclic scaffolds, thus providing access to a quick gain in C−C bond saturation.     

Aldolase Cascade Facilitated by Self-Assembled Nanotubes from Short Peptide Amphiphiles

Early evolution benefited from a complex network of reactions involving multiple C−C bond forming and breaking events that were critical for primitive metabolism. Nature gradually chose highly evolved and complex enzymes such as lyases to efficiently facilitate C−C bond formation and cleavage with remarkable substrate selectivity. Reported here is a lipidated short peptide which accesses a homogenous nanotubular morphology to efficiently catalyze C−C bond cleavage and formation. This system shows morphology-dependent catalytic rates, suggesting the formation of a binding pocket and registered enhancements in the presence of the hydrogen-bond donor tyrosine, which is exploited by extant aldolases. These assemblies showed excellent substrate selectivity and templated the formation of a specific adduct from a pool of possible adducts. The ability to catalyze metabolically relevant cascade transformations suggests the importance of such systems in early evolution.     

Transient Directing Groups in Metal−Organic Cooperative Catalysis

The direct functionalization of C−H bonds is among the most fundamental chemical transformations in organic synthesis. However, when the innate reactivity of the substrate cannot be utilized for the functionalization of a given single C−H bond, this selective C−H bond functionalization mostly relies on the use of directing groups that allow bringing the catalyst in close proximity to the C−H bond to be activated and these directing groups need to be installed before and cleaved after the transformation, which involves two additional undesired synthetic operations. These additional steps dramatically reduce the overall impact and the attractiveness of C−H bond functionalization techniques since classical approaches based on substrate pre-functionalization are sometimes still more straightforward and appealing. During the past decade, a different approach involving both the in situ installation and removal of the directing group, which can then often be used in a catalytic manner, has emerged: the transient directing group strategy. In addition to its innovative character, this strategy has brought C−H bond functionalization to an unprecedented level of usefulness and has enabled the development of remarkably efficient processes for the direct and selective introduction of functional groups onto both aromatic and aliphatic substrates. The processes unlocked by the development of these transient directing groups will be comprehensively overviewed in this review article.     

Nickel and palladium <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene complexes. Synthesis and application in cross-coupling reactions

N-Heterocyclic carbenes (NHCs) are widely used as ligands in catalysis by transition metal complexes. The catalytic activity of transition metal NHC complexes is much higher than that of the transition metal complexes bearing the phosphine and nitrogen-containing ligands. They show excellent catalytic performance in different transformations of the organic compounds, especially in the carbon—carbon and carbon—element bond forming reactions. Palladium NHC complexes are very efficient catalysts for the cross-coupling reactions. On the other hand, nickel is less expensive and regarded as a promising alternative to palladium and, therefore, it attracts increasing attention from the researches. The present review is focused on the recent advances in the synthesis of N-heterocyclic carbene complexes of nickel and palladium and their application in catalysis of cross-coupling reactions of organic, organoelement and organometallic compounds with organic halides.     

Transient and Recyclable Halogenation Coupling (TRHC) for Isoflavonoid Synthesis with Site-Selective Arylation

A transient and recyclable C−H iodination has been designed for the synthesis of isoflavonoids through the domino reactions of o-hydroxyphenyl enaminones and aryl boronic acids in the presence of catalytic KI and Pd catalyst. Instead of the conventional cross-coupling strategy employing pre-halogenated substrates, this method transforms raw C−H bond by means of a transient C−H halogenation to smoothly relay the subsequent C-arylation. Consequently, such a method avoids the pre-functionalization for C−halogen bond installation as well as the generation of stoichiometric halogen-containing waste following the cross-coupled product, disclosing an intriguing new coupling protocol to forge the C−C bond in the virgin area between classical C−X (X=halogen) bond cross coupling and the C−H activation.