Selective Functionalization of Graphene at Defect‐Activated Sites by Arylazocarboxylic tert‐Butyl Esters

The development of versatile functionalization concepts for graphene is currently in the focus of research. Upon oxo‐functionalization of graphite, the full surface of graphene becomes accessible for C?C bond formation to introduce out‐of‐plane functionality. Herein, we present the arylation of graphene with arylazocarboxylic tert‐butyl esters, which generates aryl radicals after activation with an acid. Surprisingly, the degree of functionalization is related to the concentration of lattice vacancy defects in the graphene material. Consequently, graphene materials that are free from lattice defects are not reactive. The reaction can be applied to graphene dispersed in solvents and leads to bitopic functionalization as well as monotopic functionalization when the graphene is deposited on surfaces. As the arylazocarboxylic tert‐butyl ester moiety can be attached to various molecules, the presented method paves the way to functional graphene derivatives, with the density of defects determining the degree of functionalization.     

Highly Efficient and Reversible Covalent Patterning of Graphene: 2D‐Management of Chemical Information

Patterned graphene‐functionalization with a tunable degree of functionalization can tailor the properties of graphene. Here, we present a new reductive functionalization approach combined with lithography rendering patterned graphene‐functionalization easily accessible. Two types of covalent patterning of graphene were prepared and their structures were unambiguously characterized by statistical Raman spectroscopy together with scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM‐EDS). The reversible defunctionalization processes, as revealed by temperature‐dependent Raman spectroscopy, enable the possibility to accurately modulate the degree of functionalization by annealing. This allows for the management of chemical information through complete write/store/erase cycles. Based on our strategy, controllable and efficient patterning graphene‐functionalization is no longer a challenge and facilitates the development of graphene‐based devices.     

Evolution of the electronic properties of metallic single-walled carbon nanotubes with the degree of CCl2 covalent functionalization

The changes in energetic, structural, and electronic properties of the metallic (5,5) single-walled carbon nanotube (SWNT) with the degree of sidewall covalent functionalization of CCl(2) are investigated extensively by using density functional theory calculations. The saturation concentration of CCl(2) covalent functionalization is predicted to be 33.3%. The cycloadducts always adopt an open structure. A band gap opens as the functionalization concentration reaches 11% and then basically increases with increasing functionalization concentration. These results are in agreement with available experiments and can be applied to accurately predict the band gap of metallic SWNTs produced by the HiPco method at a given CCl(2) functionalization concentration.     

Quantitative Non-Covalent Functionalization of Carbon Nanotubes

We report a convenient method for quantitative non-covalent functionalization of single-walled carbon nanotubes (SWNT) with phthalocyanine (Pc) compounds, in which a surface coverage of 49% was achieved. The effect of several process parameters on the functionalization process was elucidated. Firstly, as-produced SWNT gave the largest extent of functionalization compared with purified SWNT and as-produced multi-walled carbon nanotubes (MWNT). Secondly, the extent of functionalization was sensitive to the specific molecular structures of the Pc compounds. Finally, in terms of solvent selection, dimethylformamide (DMF) was found to give the largest extent of functionalization, which is then followed by chloroform (CHCl₃) and 1,2-dichlorobenzene (ODCB). The method reported in this paper provides new insights on the interactions between Pc molecules and carbon nanotubes and paves the way for rational control of the degree of functionalization, which is an important step from the perspective of carbon nanotube applications. Electronic supplementary material Supplementary material for this article is avilable at and is accessible for authorised users.     

Multiple Catalytic C−H Bond Functionalization for Natural Product Synthesis

In the past decade, multiple catalytic C?H bond functionalization has been successfully applied in natural product synthesis as a strategy to reduce the number of steps, increase overall yield and employ more easily available starting materials. This minireview presents selected examples making use of multiple C?H bond functionalization in conceptually different ways. First, linear syntheses are discussed, wherein multiple C?H functionalization is employed either from simple (hetero)cyclic cores, at a late stage, or to build polycyclic systems. Second, the use of multiple C?H functionalization as a strategic tool in convergent synthesis to access and couple complex fragments is discussed. Information on the scalability of the employed methods is provided when available. The presented cases indicate that multiple C?H functionalization strategies should play a great role to shape the future synthesis of functional complex molecules with improved sustainability.     

Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C—H bond activation

BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. An overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework have been provided.     

Click chemistry for high-density biofunctionalization of mesoporous silica

The applicability of click chemistry for high-density functionalization of mesoporous silica is demonstrated. The mild conditions of the copper(I)-catalyzed Huisgen reaction allow for a surface functionalization with intact biomolecules. The high covalent enzyme functionalization density under simultaneous retention of enzyme activity and the absence of leaching demonstrate the promising potential of this approach.     

Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C–H bond activation

Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic,and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. The increasing success of BODIPY dyes is closely associated with their excellent and tunable photophysical properties due to their rich functionalization chemistry.Recently, growing research efforts have been devoted to the direct functionalization of the BODIPY core,because it allows the facile installation of desired functional groups in a single atom economical step. The challenges of this direct C–H derivation come from the difficulties in finding suitable functionalization agents and proper control of the regioselectivity of the functionalization. The aim of this work is to provide an overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C–H functionalization of the BODIPY framework.     

Approaches to Pendent Groups' Functionalization of Polyimide

IntroductionPolyimide(PI) with functional pendent groupsis a specially high performance polymer,it hasplayed more and more important role in aviation,national defense,electronic device,optic communi-cation and computer systems.Since the1 990 s,various approaches(such as blending with function-al components,co- polymerization with functionalmonomers,grafting functional pendent groups)were applied to achieving functional PI materials.Compared with blending and co- polymerization,the functiona…     

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

The chemical bulk reductive covalent functionalization of thin‐layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes.     

Designed Iron Catalysts for Allylic C−H Functionalization of Propylene and Simple Olefins

Propylene gas is produced worldwide by steam cracking on million-metric-ton scale per year. It serves as a valuable starting material for π-bond functionalization but is rarely applied in transition metal-catalyzed allylic C−H functionalization for fine chemical synthesis. Herein, we report that a newly-developed cationic cyclopentadienyliron dicarbonyl complex allows for the conversion of propylene to its allylic C−C bond coupling products under catalytic conditions. This approach was also found applicable to the allylic functionalization of simple α-olefins with distinctive branched selectivity. Experimental and computational mechanistic studies supported the allylic deprotonation of the metal-coordinated alkene as the turnover-limiting step and led to insights into the multifaceted roles of the newly designed ligand in promoting allylic C−H functionalization with enhanced reactivity and stereoselectivity.     

Boron Clusters as a Platform for New Materials: Synthesis of Functionalized o‐Carborane (C2B10H12) Derivatives Incorporating DNA Fragments

A synthetic strategy for functionalization of the three vertices of o‐carborane and the attachment of the obtained triped to the solid support was developed. Further functionalization of the triped with short DNA sequences by automated DNA synthesis was achieved. The proposed methodology is a first example of boron cluster chemistry on a solid support opening new perspectives in boron cluster functionalization.     

Redox‐Neutral α,β‐Difunctionalization of Cyclic Amines

In contrast to the continuously growing number of methods that allow for the efficient α‐functionalization of amines, few strategies exist that enable the direct functionalization of amines in the β‐position. A general redox‐neutral strategy is outlined for amine β‐functionalization and α,β‐difunctionalization that utilizes enamines generated in situ. This concept is demonstrated in the context of preparing polycyclic N,O‐acetals from simple 1‐(aminomethyl)‐β‐naphthols and 2‐(aminomethyl)‐phenols.     

Overcoming the insolubility of carbon nanotubes through high degrees of sidewall functionalization

The use of carbon nanotubes in materials applications has been slowed due to nanotube insolubility and their incompatibility with polymers. We recently developed two protocols to overcome the insoluble nature of carbon nanotubes by affixing large amounts of addends to the nanotube sidewalls. Both processes involve reactions with aryl diazonium species. First, solvent-free functionalization techniques remove the need for any solvent during the functionalization step. This delivers functionalized carbon nanotubes with increased solubility in organic solvents and processibility in polymeric blends. Additionally, the solvent-free functionalization process can be done on large scales, thereby paving the way for use in bulk applications such as in structural materials development. The second methodology involves the functionalization of carbon nanotubes that are first dispersed as individual tubes in surfactants within aqueous media. The functionalization then ensues to afford heavily functionalized nanotubes that do not re-rope. They remain as individuals in organic solvents giving enormous increases in solubility. This protocol yields the highest degree of functionalization we have obtained thus far-up to one in nine carbon atoms on the nanotube has an organic addend. The proper characterization and solubility determinations on nanotubes are critical; therefore, this topic is discussed in detail.     

配体促进的过渡金属催化芳烃远程meta-C—H键官能化反应研究进展

过渡金属催化C—H活化反应中,配体能够对催化中心的空间及电子效应进行调控,从而实现芳烃C—H键的选择性官能化.近年来,配体促进芳烃远程C—H键官能化反应研究有了新的进展.对近几年来配体促进的过渡金属催化芳烃远程meta-C—H键选择性官能化反应进行了系统总结,并对该研究领域的局限性和未来的发展前景进行总结和展望.     

光/电化学氧化诱导C–H键官能团化

C–H键活化及其官能团化一直被认为是合成化学的圣杯,光/电氧化诱导C–H键官能团化反应为追求更为绿色、原子经济性、步骤经济性更高的现代合成化学提供了新思路.我们借助可见光或电化学氧化诱导策略实现了直接C–H键官能团化,即底物无需预官能团化,无需外加氧化剂,可直接实现碳–碳以及碳–杂键的构建.通过光/电化学氧化诱导策略使得反应在更为温和的条件下进行,能够兼容更多官能团,并且为合成化学提供一条新的途径.近些年,该策略已经应用于不同化学环境C–H官能团化构建多种化学键.本文结合该领域的代表性工作,重点介绍本课题组近些年在光/电氧化诱导C–H键官能团化反应上的研究进展,并对这一领域的前景进行了展望.     

Transition‐Metal‐Catalyzed Redox‐Neutral and Redox‐Green C–H Bond Functionalization

Transition‐metal‐catalyzed C–H bond functionalization has become one of the most promising strategies to prepare complex molecules from simple precursors. However, the utilization of environmentally unfriendly oxidants in the oxidative C–H bond functionalization reactions reduces their potential applications in organic synthesis. This account describes our recent efforts in the development of a redox‐neutral C–H bond functionalization strategy for direct addition of inert C–H bonds to unsaturated double bonds and a redox‐green C–H bond functionalization strategy for realization of oxidative C–H functionalization with O₂ as the sole oxidant, aiming to circumvent the problems posed by utilizing environmentally unfriendly oxidants. In principle, these redox‐neutral and redox‐green strategies pave the way for establishing new environmentally benign transition‐metal‐catalyzed C–H bond functionalization strategies.     

Site‐Selective Oxidation of Monolayered Liquid‐Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile

In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS₂ with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS₂ is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.     

Strategies for the Controlled Covalent Double Functionalization of Graphene Oxide

Graphene oxide (GO) is a versatile platform with unique properties that have found broad applications in the biomedical field. Double functionalization is a key aspect in the design of multifunctional GO with combined imaging, targeting, and therapeutic properties. Compared to noncovalent functionalization, covalent strategies lead to GO conjugates with a higher stability in biological fluids. However, only a few double covalent functionalization approaches have been developed so far. The complexity of GO makes the derivatization of the oxygenated groups difficult to control. The combination of a nucleophilic epoxide ring opening with the derivatization of the hydroxyl groups through esterification or Williamson reaction was investigated. The conditions were selective and mild, thus preserving the structure of GO. Our strategy of double functionalization holds great potential for different applications in which the derivatization of GO with different molecules is needed, especially in the biomedical field.     

meta-Selective C−H Functionalization of Pyridines

The pyridine moiety is an important core structure for a variety of drugs, agrochemicals, catalysts, and functional materials. Direct functionalization of C−H bonds in pyridines is a straightforward approach to access valuable substituted pyridines. Compared to the direct ortho- and para-functionalization, meta-selective pyridine C−H functionalization is far more challenging due to the inherent electronic properties of the pyridine entity. This review summarizes currently available methods for pyridine meta-C−H functionalization using a directing group, non-directed metalation, and temporary dearomatization strategies. Recent advances in ligand control and temporary dearomatization are highlighted. We analyze the advantages as well as limitations of current techniques and hope to inspire further developments in this important area.