Direct synthesis of haloaromatics from nitroarenes via a sequential one-pot Mo-catalyzed reduction/Sandmeyer reaction.

Herein, we report the direct synthesis of a wide variety of functionalized aromatic bromides, chlorides, iodides, and fluorides from nitroarenes in a sequential one-pot operation. This protocol is based on an air- and moisture-tolerant dioxomolybdenum-catalyzed reduction of nitroaromatics, employing pinacol as a reducing agent, which enables subsequent diazotization and halogenation steps. This methodology represents a step-economical, practical, and alternative procedure for synthesizing haloaromatics directly from nitroaromatics.

Synthesis of 1,4-ketoaldehydes and 1,4-diketones by Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols.

A new two-step procedure for the synthesis of 1,4-dicarbonyls has been developed involving an efficient and clean Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols with DMSO, which is used as solvent and oxidant. The required starting glycols were prepared by nucleophilic additions of organolithiums and Grignard reagents to easily available 2-hydroxycyclobutanones.

Mo-Catalyzed One-Pot Synthesis of N-Polyheterocycles from Nitroarenes and Glycols with Recycling of the Waste Reduction Byproduct. Substituent-Tuned Photophysical Properties.

A catalytic domino reduction-imine formation-intramolecular cyclization-oxidation for the general synthesis of a wide variety of biologically relevant N-polyheterocycles, such as quinoxaline- and quinoline-fused derivatives, and phenanthridines, is reported. A simple, easily available, and environmentally friendly dioxomolybdenum(VI) complex has proven to be a highly efficient and versatile catalyst for transforming a broad range of starting nitroarenes involving several redox processes. Not only is this a sustainable, step-economical as well as air- and moisture-tolerant method, but also it is worth highlighting that the waste byproduct generated in the first step of the sequence is recycled and incorporated in the final target molecule, improving the overall synthetic efficiency. Moreover, selected indoloquinoxalines have been photophysically characterized in cyclohexane and toluene with exceptional fluorescence quantum yields above 0.7 for the alkyl derivatives.

Phyllosilicate-content influence on the spectroscopic properties and antioxidant capacity of Iberian Cretaceous clays.

Kaolinite-rich Cretaceous clay sediment samples from Burgos (Spain) have been analyzed by elemental analysis, X-ray fluorescence, inductively coupled plasma mass spectrometry, X-ray diffraction and different spectroscopic techniques, as Fourier Transform Infrared, ultraviolet-visible and electron paramagnetic resonance. The clay sediment samples mainly contain quartz, muscovite and kaolinite. Different radicals, as A- and B-Centers in kaolinite and organic paramagnetic species, are detected. An illite/kaolinite FTIR band ratio parameter (IKB) is proposed to infer the illite/kaolinite proportion, which can be useful to graphically visualize the iron-substituted Al(III) sites. Studies of the activity as scavengers of DPPH and ABTS radicals show that samples with a larger amount of orthorhombic Fe(III) ions replacing Al(III) ions exhibit a higher antioxidant capacity.

Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds.

The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C-N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.