Tris(pentafluorophenyl)borane and beyond: modern advances in borylation chemistry

As main-group chemistry, in particular boron chemistry, has expanded and developed over the past 20 years, one reagent has risen to prominence as well. Tris(pentafluorophenyl)borane, B(C6F5)3 (commonly known as BCF), has demonstrated extensive applications in a wide variety of reactions, including borylation, hydrogenation, hydrosilylation, frustrated Lewis pair (FLP) chemistry, Lewis acid catalysis, and more. The high Lewis acidity of B(C6F5)3 is derived from the electronic effects of its three C6F5 rings, rendering it a versatile reagent for a great number of reactions. In addition, the steric bulk of these rings also allows it to function as the Lewis acid in a FLP, granting this reagent yet another synthetically useful application. However, as main-group chemistry continues to evolve as a field, new reagents are required that go beyond BCF, increasing not only the range of reactions available but also the breadth of compounds attainable. Great strides have already been made in order to accomplish this task, and this review will highlight modern advances in boron chemistry relating to borylation reactions. Herein, we will show the recent uses of B(C6F5)3 in borylation reactions while also focusing on current advances in novel borane and borocation usage that eclipses that of the stalwart B(C6F5)3

The cell adhesion protein CAR is a negative regulator of synaptic transmission

The Coxsackievirus and adenovirus receptor (CAR) is essential for normal electrical conductance in the heart, but its role in the postnatal brain is largely unknown. Using brain specific CAR knockout mice (KO), we discovered an unexpected role of CAR in neuronal communication. This includes increased basic synaptic transmission at hippocampal Schaffer collaterals, resistance to fatigue, and enhanced long-term potentiation. Spontaneous neurotransmitter release and speed of endocytosis are increased in KOs, accompanied by increased expression of the exocytosis associated calcium sensor synaptotagmin 2. Using proximity proteomics and binding studies, we link CAR to the exocytosis machinery as it associates with syntenin and synaptobrevin/VAMP2 at the synapse. Increased synaptic function does not cause adverse effects in KO mice, as behavior and learning are unaffected. Thus, unlike the connexin-dependent suppression of atrioventricular conduction in the cardiac knockout, communication in the CAR deficient brain is improved, suggesting a role for CAR in presynaptic processes

Structures of tetrasilylmethane derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the gas phase, and their dynamic structures in solution

The structures of the molecules (XMe2Si)2C(SiMe3)2, where X = H, Cl, Br, have been determined by gas electron diffraction (GED) using the SARACEN method of restraints, with all analogues existing in the gas phase as mixtures of C1- and C2-symmetric conformers. Variable temperature 1H and 29Si solution-phase NMR studies, as well as 13C NMR and 1H/29Si NMR shift correlation and 1H NMR saturation transfer experiments for the chlorine and bromine analogues, are reported. At low temperatures in solution there appear to be two C1 conformers and two C2 conformers, agreeing with the isolated-molecule calculations used to guide the electron diffraction refinements. For (HMe2Si)2C(SiMe3)2 the calculations indicated six conformers close in energy, and these were modeled in the GED refinement

Insertion and Substitution Chemistry at the Boron Fourth Position in Charge-Neutral Zwitterionic Tripodal Tris(methimazolyl)borate Ligands

A number of new charge-neutral zwitterionic tris(methimazolyl)borate ligands have been synthesized, either by substitution of the dimethylamine group in the adduct (dimethylamine)tris(methimazolyl)borane (1) or by insertion into its B–N(dimethylamine) bond by an unsaturated Lewis base. Two new anionic ligands, (thiocyanato)tris(methimazolyl)borate and (cyano)tris(methimazolyl)borate, have also been accessed by this method