Reductive Catenation of Phosphine Antimony Complexes

Reactions of triarylphosphines with fluoroantimony(III) triflates give phosphine antimony(III) complexes, which undergo spontaneous reductive elimination of fluorophosphonium cations. The resulting phosphine antimony(I) complexes catenate to give the first examples of cationic antimony bicyclic compounds, [(R₃P)₄Sb₆]⁴⁺, featuring a bicyclo[3.1.0]hexastibine framework stabilized by four phosphine ligands. The unprecedented 14‐electron redox process illustrates the generality of the reductive catenation method.     

Tandem Chemoselective Suzuki–Miyaura Cross‐Coupling Enabled by Nucleophile Speciation Control

Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki–Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two C? C bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks.     

Controlled Light‐Mediated Preparation of Gold Nanoparticles by a Norrish Type I Reaction of Photoactive Polymers

Gold nanoparticles (AuNPs) are subjects of broad interest in scientific community due to their promising physicochemical properties. Herein we report the facile and controlled light‐mediated preparation of gold nanoparticles through a Norrish type I reaction of photoactive polymers. These carefully designed polymers act as reagents for the photochemical reduction of gold ions, as well as stabilizers for the in situ generated AuNPs. Manipulating the length and composition of the photoactive polymers allows for control of AuNP size. Nanoparticle diameter can be controlled from 1.5 nm to 9.6 nm.     

Increased Water Reduction Efficiency of Polyelectrolyte‐Bound Trimetallic [Ru,Rh,Ru] Photocatalysts in Air‐Saturated Aqueous Solutions

The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H₂ production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)₂Ru(BL)}₂RhX₂]⁵⁺ (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air‐saturated aqueous solution because of the quenching of the metal‐to‐ligand charge‐transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4‐styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)₂Ru(dpp)}₂RhCl₂]⁵⁺ (bpy=2,2′‐bipyridine, dpp=2,3‐bis(2‐pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H₂ production over three times that of deoxygenated aqueous solutions alone. H₂ photocatalysis proceeds even under aerobic conditions for PSS‐containing solutions, an exciting consequence for solar hydrogen‐production research.     

Short,Enantioselective Total Synthesis of Chatancin

An enantioselective total synthesis of the polycyclic diterpene (+)‐chatancin, a potent PAF antagonist, is reported. Proceeding in seven steps from dihydrofarnesal, this synthetic route was designed to circumvent macrocyclization‐based strategies to complex, cyclized cembranoids. The described synthesis requires only six chromatographic purifications, is high yielding, and avoids protecting‐group manipulations. An X‐ray crystal structure of this fragile marine natural product was obtained.     

Oxidative Deselenization of Selenocysteine: Applications for Programmed Ligation at Serine

Despite the unique chemical properties of selenocysteine (Sec), ligation at Sec is an under‐utilized methodology for protein synthesis. We describe herein an unprecedented protocol for the conversion of Sec to serine (Ser) in a single, high‐yielding step. When coupled with ligation at Sec, this transformation provides a new approach to programmed ligations at Ser residues. This new reaction is compatible with a wide range of functionality, including the presence of unprotected amino acid side chains and appended glycans. The utility of the methodology is demonstrated in the rapid synthesis of complex glycopeptide fragments of the epithelial glycoproteins MUC5AC and MUC4 and through the total synthesis of the structured, cysteine (Cys)‐free protein eglin C.