A solvent dependent C(sp3)-CF3 bond-forming reductive elimination from neutral four-coordinate Cu(III) complexes [(L)CuIII(CF3)2(CH2CO2tBu)] (L=pyridine or its derivatives) is described. Reactions in less polar solvent ClCH2CH2Cl proceed via a concerted bond breaking/bond forming process along with the reorientation of the ligand, while reaction in polar solvent DMF occurs via a rate limiting ligand-dissociation, followed by C(sp3)-CF3 reductive elimination from the resulting three-coordinate intermediate. These mechanistic proposals are supported by kinetic studies that included ligand and temperature effects, as well as DFT calculations.

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range of cyclic or acyclic quaternary carbon centers under mild conditions. The utilization of the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using a bulky chiral diimine as the ligand for the Ni catalyst, quaternary carbon stereocenters can be readily prepared with high levels of enantiocontrol. Mechanism studies suggest that, before protonation, a rare nickel shift from alkyl nickel to aryl nickel might occur.

In recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional asymmetric transition metal catalysis, particularly those related to the use of redox-active chemical reagents. Furthermore, the redox potentials of molecular electrocatalysts can be conveniently tuned by modifying their ligands, thereby governing the reaction regioselectivity and stereoselectivity. As a result, the AOES has emerged as a powerful and promising tool for the synthesis of chiral compounds.In this Account, we summarize and contextualize our recent efforts in the field of AOES. Our primary strategy involves leveraging the controllability of electrochemical potential and current to regulate the oxidation state of organometallics, thereby facilitating the desired reactions. An efficient asymmetric synthesis platform was established under mild conditions, significantly reducing the reliance on chemical redox reagents. Our research has been systematically categorized into three sections based on distinct electrolysis modes: asymmetric transition metal catalysis combined with anodic oxidation, cathodic reduction, and paired electrolysis. In each section, we highlight our innovative discoveries tailored to the unique characteristics of the respective electrolysis modes.In many transformations, transition metal-catalyzed reactions involving traditional chemical redox reagents and those utilizing electrochemistry exhibit similar reactivities. However, we also observed notable differences in certain cases. These findings include the following: (1) Enhanced efficiency in asymmetric electrochemical synthesis: for instance, the Rh-catalyzed enantioselective electrochemical functionalization of C-H bonds demonstrates superior efficiency. (2) Expanded scope of transformations: certain transformations, previously challenging in traditional transition metal catalysis, can be achieved through electrochemistry due to the tunability of redox potentials. A notable example is the enantioselective reductive coupling of aryl chlorides, which significantly expands the range of accessible transformations. Additionally, our mechanistic studies explore unique techniques intrinsic to electrochemistry, such as controlled potential electrolysis experiments, the impact of electrode materials on catalyst performance, and cyclic voltammetry studies. These investigations provide a more intuitive understanding of the behavior of metal catalysts through the study of electrochemical mechanisms, which can also guide the design of new catalytic systems.The advancements in this field offer a robust platform for environmentally friendly and sustainable selective asymmetric transformations. By integrating electrochemistry with transition metal catalysis, we have developed a versatile approach for organic synthesis that not only enhances the efficiency and selectivity of reactions but also reduces the environmental impact. We anticipate that this Account will stimulate further research and innovation in the realm of AOES, leading to the discovery of new catalytic systems and the development of more sustainable synthetic methodologies.

Transparent wood with high transmittance and versatility has attracted great attention as an energy-saving building material. Many studies have focused on luminescent transparent wood, while the research on organic afterglow transparent wood is an interesting combination. Here, we use luminescent difluoroboron beta-diketonate (BF2bdk) compounds, methyl methacrylate (MMA), delignified wood, and initiators to prepare room-temperature phosphorescent transparent wood by thermal initiation polymerization. The resultant PMMA has been found to interact with BF2bdk via dipole-dipole interactions and consequently enhance the intersystem crossing of BF2bdk excited states. The transparent wood matrix can provide a rigid environment for BF2bdk triplets and serve as oxygen barrier to suppress non-radiative decay and oxygen quenching. The prepared afterglow material has the characteristics of diverse composition, long afterglow emission lifetimes, and high photoluminescence quantum yield. This afterglow transparent wood also demonstrates potential application value in areas such as high mechanical strength, good hydrophobicity, and high cost-effectiveness.

A visible-light-induced intramolecular crossed [2+2] cycloaddition reaction of allene-tethered alkylidenecyclopropanes was reported in this paper. The reactions were conducted under mild conditions using Iridium(III) catalyst FirPic as a photosensitizer for energy transfer, affording bridged bicyclic alkenes in moderate to good yields with excellent regioselectivity and stereoselectivity through the regulation of substituents at the olefin's terminal position. Meanwhile, the computational study explained the special region control assisted by sulfonyl radicals in detail.

Considering the unique electronic properties of the CF2 and the CN groups, the CF2CN group has significant potential in drug and agrochemical development, as well as material sciences. However, incorporating a CF2CN group remains a considerable challenge. In this work, we disclose a use of bromodifluoroacetonitrile (BrCF2CN), a cost-effective and readily available reagent, as a radical source for cyanodifluoromethylation of alkyl alkenes, aryl alkenes, alkynes, and (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope and remarkable tolerance to various functional groups. Notably, the cyanodifluoromethylation of alkynes predominantly provides sterically hindered alkenes, a thermodynamically unfavorable outcome, and (hetero)arene C-H bonds are directly amenable to cyanodifluoromethylation without pre-functionalization.

The unprecedent gold-catalyzed intermolecular 1,2-difunctionalization of nitriles with o-iodophenols or o-iodoanilines via Au(I)/Au(III) redox catalysis has been developed, providing an expedient route to the synthesis of benzoxazoles or benzimidazoles with broad substrate scope and high functional compatibility. Mechanistic investigation reveals that the Au(III)-Ar species generated via oxidative addition of o-iodophenol to MeDalphosAu+, serves as a key intermediate. Particularly, this annulation is initiated by oxidative addition, rather than the nucleophilic attack of the phenol moiety in o-iodophenol towards the nitrile. The method was also applied to the synthesis of poly aza-heterocycles via a cascade Au(I)/Au(III) and Au(I) catalysis relay.

Three-dimensional (3-D) pi-conjugated-polymer-containing nanostructures of well-controlled composition/dimension exhibit promising applications in fields from nanomedicine to microelectronics. However, it remains a great challenge to easily and efficiently prepare hierarchical 3-D nanostructures in a controlled manner. In this work, we develop a one-step/one-pot strategy to generate flower-like nanostructures containing a core and numerous uniform nanofibers protruding from the central core by crystallization-driven co-self-assembly of OPE9-b-P2VP56 [OPE = oligo(p-phenylene ethynylene); P2VP = poly(2-vinylpyridine); subscript represents the degree of polymerization] and poly(styrene sulfonic acid) (PSS) with a direct heating-cooling protocol. It is disclosed that the hydrogen bonding interactions between pyridyls of P2VP and -SO3H units of PSS not only accelerated the aggregation of OPE9-b-P2VP56 unimers but also led to intermicellar aggregation of initially formed micelles driven by the solvophobic effect of complexes of P2VP/PSS domains upon cooling. Subsequently, unimers continued to deposit from exposed ends of nanofibers to give flower-like nanostructures. By variation of the content of OPE9-b-P2VP56 and mass ratio of PSS to OPE9-b-P2VP56, the length and number of nanofibers protruding from the core can be regulated. More importantly, the ends of protruding nanofibers remained active toward unimer deposition for further micellar elongation to afford flower-like nanostructures with segmented diblock nanofibers. In addition, the surface of protruding nanofibers can be further coated with Ag nanoparticles to give hybrid nanostructures by taking advantage of the coordinating capacity of pyridyls of P2VP chains. Given the excellent applicability of CDSA on diverse pi-conjugated polymers, this work opens a new avenue to create diverse pi-conjugated-polymer-based 3-D nanostructures in a controlled way.

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success in (asymmetric) alpha-functionalization of carbonyl compounds. However, examples on the use of this activation mode in the transformations of other functional groups are rare, and the combination of SOMO activation with transition metal catalysis is still less explored. In the area of deoxygenative functionalization of amides, intermediates such as iminium ions and enamines were often generated in situ to result in the formation of alpha-functionalized amines. In contrast, the direct deoxygenation of amides to beta-functionalized amines is highly appealing yet remains scarcely investigated. Here, a deoxygenative arylation of amides with aryl halides was developed via multicatalysis of iridium/photoredox/nickel/iridium, affording beta-aryl amines in high efficiency. The key to the success of this reaction is the SOMO activation of enamine in synergy with a Ni-catalyzed arylation, which is in conjunction with two compatible Ir-catalyzed reduction processes.

The pseudokinase HER3 emerges as a promising anti-cancer target, especially for HER2-driven breast cancer and EGFR-mediated non-small cell lung cancer. However, it is challenging to target HER3 by ATP-competitive small molecules because HER3 is catalytically impaired. Herein, we report the discovery of a series of HER3 degraders by connecting a HER3 binder bosutinib with a hydrophobic tag adamantane. The optimal compound CZY43 effectively induced HER3 degradation in dose- and time-dependent manners in breast cancer SKBR3 cells. Mechanistic studies revealed compound CZY43 to induce HER3 degradation via autophagy. Importantly, compound CZY43 potently inhibited HER3-dependent signaling, cancer cell growth and cell adhesion, and was more potent than bosutinib. This study further suggested that HER3 can be modulated by small-molecule degraders, and compound CZY43 can serve as a lead compound for further optimization.