Amine catalysis for the organocatalytic diboration of challenging alkenes

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The generation of in situ sp 2 –sp 3 diboron adducts has revolutionised the synthesis of organoboranes. Organocatalytic diboration reactions have represented a milestone in terms of unpredictable reactivity of these adducts. However, current methodologies have limitations in terms of substrate scope, selectivity and functional group tolerance. Here a new methodology based on the use of simple amines as catalyst is reported. This methodology provides a completely selective transformation overcoming current substrate scope and functional/protecting group limitations. Mechanistic studies have been included in this report

Zn⁺-O⁻ dual-spin surface states formation by modification of ZnO nanoparticles with diboron compounds

ZnO semiconductor oxides are versatile functional materials that are used in photoelectronics, catalysis, sensing, etc. The Zn⁺–O⁻ surface electronic states of semiconductor oxides were formed on the ZnO surface by Zn 4s and O 2p orbital coupling with the diboron compound’s B 2p orbitals. The formation of spin-coupled surface states was based on the spin–orbit interaction on the interface, which has not been reported before. This shows that the semiconductor oxide’s spin surface states can be modulated by regulating surface orbital energy. The Zn⁺–O⁻ surface electronic states were confirmed by electron spin resonance results, which may help in expanding the fundamental research on spintronics modulation and quantum transport

Modification of TiO_2 Nanoparticles with Organodiboron Molecules Inducing Stable Surface Ti^(3+) Complex

As one of the most promising semiconductor oxide materials, titanium dioxide (TiO_2) absorbs ultraviolet (UV) light but not visible light. To address this limitation, the introduction of Ti^(3+) defects represents a common strategy to render TiO_2 visible-light-responsive. Unfortunately, current hurdles in Ti^(3+) generation technologies impeded the widespread application of Ti^(3+) modified materials. Herein, we demonstrate a simple and mechanistically distinct approach to generating abundant surface-Ti^(3+) sites without leaving behind oxygen vacancy and sacrificing one-off electron donors. In particular, upon adsorption of organodiboron reagents onto TiO_2 nanoparticles, spontaneous electron injection from the dibron-bound O^(2-) site to adjacent Ti^(4+) site leads to an extremely stable blue surface Ti^(3+)‒O^(-•) complex. Notably, this defect generation protocol is also applicable to other semiconductor oxides including ZnO, SnO_2, Nb_2O_5 and In_2O_3. Furthermore, the as-prepared photoelectronic device using this strategy affords 10^3 fold higher visible light response, and the fabricated perovskite solar cell shows an enhanced performance

Atropselective syntheses of (-) and (+) rugulotrosin A utilizing point-to-axial chirality transfer

Chiral, dimeric natural products containing complex structures and interesting biological properties have inspired chemists and biologists for decades. A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the requisite 2,2'-biaryl linkage. Highly selective point-to-axial chirality transfer was achieved using palladium catalysis with achiral phosphine ligands. Single X-ray crystal diffraction data were obtained to confirm both the atropisomeric configuration and absolute stereochemistry of rugulotrosin A. Computational studies are described to rationalize the atropselectivity observed in the key dimerization step. Comparison of the crude fungal extract with synthetic rugulotrosin A and its atropisomer verified that nature generates a single atropisomer of the natural product.P50 GM067041 - NIGMS NIH HHS; R01 GM099920 - NIGMS NIH HHS; GM-067041 - NIGMS NIH HHS; GM-099920 - NIGMS NIH HH

An experimental and theoretical study into the facile, homogenous (N-Heterocyclic Carbene)2-Pd(0) catalyzed diboration of internal and terminal alkynes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Pd(ITMe)(2)(PhC CPh) acts as a highly reactive pre-catalyst in the unprecedented homogenous catalyzed diboration of terminal and internal alkynes, yielding a number of novel and known syn-1,2-diborylalkenes in a 100% stereoselective manner. DFT calculations suggest that a similar reaction pathway to that proposed for platinum phosphine analogues is followed, and that destabilization of key intermediates by the NHCs is vital to the overall success for the palladium-catalyzed B-B addition to alkynes.62074617467EPSRC Standard Research Student (DTG) [EP/L505109/1]Fundacao de Amparo a Pesquisa do Estado de Sao Paulo [2013/04813-6, 2015/11840-5, 2015/01491-3]Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Nox2 redox signaling maintains essential cell populations in the brain.

Reactive oxygen species (ROS) are conventionally classified as toxic consequences of aerobic life, and the brain is particularly susceptible to ROS-induced oxidative stress and damage owing to its high energy and oxygen demands. NADPH oxidases (Nox) are a widespread source of brain ROS implicated in seizures, stroke and neurodegeneration. A physiological role for ROS generation in normal brain function has not been established, despite the fact that mice and humans lacking functional Nox proteins have cognitive deficits. Using molecular imaging with Peroxyfluor-6 (PF6), a new selective fluorescent indicator for hydrogen peroxide (H(2)O(2)), we show that adult hippocampal stem/progenitor cells (AHPs) generate H(2)O(2) through Nox2 to regulate intracellular growth signaling pathways, which in turn maintains their normal proliferation in vitro and in vivo. Our results challenge the traditional view that brain ROS are solely deleterious by demonstrating that controlled ROS chemistry is needed for maintaining specific cell populations

Influence of Phosphoramidites in Copper-Catalyzed Conjugate Borylation Reaction

Copper(I) has become the preferred metal to catalyze the β-boration of α,β-unsaturated carbonyl compounds, and now we demonstrate that easily accessible monodentate chiral ligands, such as phosphoramidites and phosphites, can be convenient alternative ligands to induce asymmetry in the enantioselective version of this reaction, particularly in the β-boration of α,β-unsaturated imines.