A Two‐Photon H2O2‐Activated CO Photoreleaser

Carbon monoxide (CO) is proposed as an active pharmaceutical agent with promising pharmaceutical prospects, as it has been involved in multifaceted modulation of diverse physiological and pathological processes. However, questions remain for therapeutic application of inhaled CO attributed to the inherent great affinity between CO and hemoglobin. Therefore, a robust platform with the function of CO transport and controllable release, depending on the local status of an organism, is of prominent significance for effectively avoiding the side effects of CO inhalation and optimizing the biological regulation function of CO. Utilizing the oxidative stress biomarker H₂O₂ as a trigger and combining with photo‐control, a two‐photon H₂O₂‐activated CO photoreleaser, FB, featuring highly sensitive and specific H₂O₂ sensing and photocontrollable CO release, was developed and the vasodilation effect of CO against angiotensin II was demonstrated.     

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

The first visible‐light‐mediated synthesis of trifluoromethylselenolated arenes under metal‐free conditions is reported. The use of an organic photocatalyst enables the trifluoromethylselenolation of arene diazonium salts using the shelf‐stable reagent trifluoromethyl tolueneselenosulfonate at room temperature. The reaction does not require the presence of any additives and shows high functional‐group tolerance, covering a very broad range of starting materials. Mechanistic investigations, including EPR spectroscopy, luminescence investigations, and cyclic voltammetry allow rationalization of the reaction mechanism.     

Stress‐Transfer‐Induced In Situ Formation of Ultrathin Nickel Phosphide Nanosheets for Efficient Hydrogen Evolution

Ultrathin two‐dimensional (2D) nanostructures have attracted increasing research interest for energy storage and conversion. However, tackling the key problem of lattice mismatch inducing the instability of ulreathin nanostructures during phase transformations is still a critical challenge. Herein, we describe a facile and scalable strategy for the growth of ultrathin nickel phosphide (Ni₂P) nanosheets (NSs) with exposed (001) facets. We show that single‐layer functionalized graphene with residual oxygen‐containing groups and a large lateral size contributes to reducing the lattice strain during phosphorization. The resulting nanostructure exhibits remarkable hydrogen evolution activity and good stability under alkaline conditions.     

Antimony‐Functionalized Phosphine‐Based Photopolymer Networks

The synthesis of phosphane‐ene photopolymer networks, where the networks are composed of crosslinked tertiary alkyl phosphines are reported. Taking advantage of the rich coordination chemistry of alkyl phosphines, stibino‐phosphonium and stibino‐bis(phosphonium) functionalized polymer networks could be generated. Small‐molecule stibino‐phosphonium and stibino‐bis(phosphonium) compounds have been well characterized previously and were used as models for spectroscopic comparison to the macromolecular analogues by NMR and XANES spectroscopy. This work reveals that the physical and electronic properties of the materials can be tuned depending on the type of coordination environment. These materials can be used as ceramic precursors, where the Sb‐functionalized polymers influence the composition of the resulting ceramic.     

Modular One‐Step Three‐Component Synthesis of Tetrahydroisoquinolines Using a Catellani Strategy

Reported is a modular one‐step three‐component synthesis of tetrahydroisoquinolines using a Catellani strategy. This process exploits aziridines as the alkylating reagents, through palladium/norbornene cooperative catalysis, to enable a Catellani/Heck/aza‐Michael addition cascade. This mild, chemoselective, and scalable protocol has broad substrate scope (43 examples, up to 90 % yield). The most striking feature of this protocol is the excellent regioselectivity and diastereoselectivity observed for 2‐alkyl‐ and 2‐aryl‐substituted aziridines to access 1,3‐cis‐substituted and 1,4‐cis‐substituted tetrahydroisoquinolines, respectively. Moreover, this is a versatile process with high step and atom economy.     

Nanobodies: Chemical Functionalization Strategies and Intracellular Applications

Nanobodies can be seen as next‐generation tools for the recognition and modulation of antigens that are inaccessible to conventional antibodies. Due to their compact structure and high stability, nanobodies see frequent usage in basic research, and their chemical functionalization opens the way towards promising diagnostic and therapeutic applications. In this Review, central aspects of nanobody functionalization are presented, together with selected applications. While early conjugation strategies relied on the random modification of natural amino acids, more recent studies have focused on the site‐specific attachment of functional moieties. Such techniques include chemoenzymatic approaches, expressed protein ligation, and amber suppression in combination with bioorthogonal modification strategies. Recent applications range from sophisticated imaging and mass spectrometry to the delivery of nanobodies into living cells for the visualization and manipulation of intracellular antigens.     

Catalytic Asymmetric Functionalization of Aromatic CH Bonds by Electrophilic Trapping of Metal‐Carbene‐Induced Zwitterionic Intermediates

Asymmetric functionalization of aromatic C? H bonds of N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α‐diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This Rh^II/chiral phosphoric acid cocatalyzed transformation is proposed to proceed through a metal‐carbene‐induced zwitterionic intermediate which undergoes electrophilic trapping. To the best of our knowledge, this is the first asymmetric example of metal carbene‐induced intermolecular functionalization of aryl C? H bonds.     

Gold(I)‐Catalyzed Diazo Coupling: Strategy towards Alkene Formation and Tandem Benzannulation

A gold(I)‐catalyzed cross‐coupling of diazo compounds to afford tetrasubstituted alkenes has been developed by taking advantage of a trivial electronic difference between two diazo substrates. A N‐heterocyclic‐carbene‐derived gold complex is the most effective catalyst for this transformation. Based on this new strategy, a gold(I)‐initiated benzannulation has been achieved through a tandem reaction involving a diazo cross‐coupling, 6π electrocyclization, and oxidative aromatization.     

An Ylide Transformation of Rhodium(I) Carbene: Enantioselective Three‐Component Reaction through Trapping of Rhodium(I)‐Associated Ammonium Ylides by β‐Nitroacrylates

The chiral Rh^I–diene‐catalyzed asymmetric three‐component reaction of aryldiazoacetates, aromatic amines, and β‐nitroacrylates was achieved to obtain γ‐nitro‐α‐amino‐succinates in good yields and with high diastereo‐ and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of Rh^I‐associated ammonium ylides by nitroacrylates. This new transformation represents the first example of Rh^I‐carbene‐induced ylide transformation.     

Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)H and C(sp2)H Functionalization Reactions

Assoanine, pratosine, hippadine, and dehydroanhydrolycorine belong to the pyrrolophenanthridine family of alkaloids, which are isolated from plants of the Amaryllidaceae species. Structurally, these alkaloids are characterized by a tetracyclic skeleton that contains a biaryl moiety and an indole core, and compounds belonging to this class have received considerable interest from researchers in a number of fields because of their biological properties and the challenges associated with their synthesis. Herein, a strategy for the total synthesis of these alkaloids by using C? H activation chemistry is described. The tetracyclic skeleton was constructed in a stepwise manner by C(sp³)? H functionalization followed by a Catellani reaction, including C(sp²)? H functionalization. A one‐pot reaction involving both C(sp³)? H and C(sp²)? H functionalization was also attempted. This newly developed strategy is suitable for the facile preparation of various analogues because it uses simple starting materials and does not require protecting groups.