Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines

A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd⁰‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials.     

Transition‐Metal‐Free Trifluoromethylthiolation of N‐Heteroarenes

A general and efficient methodology for the direct transition metal free trifluoromethylthiolation of a broad range of biologically relevant N‐heteroarenes is reported employing abundant sodium chloride as the catalyst. This method is operationally simple, exhibits high functional group tolerance, and does not require protecting groups.     

Design of organophosphorus materials for organic electronics and bio-applications

π-Extended molecules are key components for the development of materials science. In fact, polyaromatic structures are fundamental for the scientific and technological progress of fields such as organic electronics and bio-applications. Beneficial properties of π-extended structures are absorption in the visible region, often luminescence, high electron mobilities and stability. Common approaches to adjust the properties of polyaromatic structures to functional setups involve changes in shape and size at the molecular level. Recently, incorporating hetero-elements emerged as successful approach. In this regard, organophosphorus conjugated molecules are new materials holding great promise for potential applications. In this review, we comprehensively discuss the design/development of polyaromatic phosphorus materials and their applicability. We establish structure/property/applicability relationships to provide key guidelines for the engineering of newer, future applications. This article thus provides a source of information for the further development of this rapidly evolving field of research.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

All Non-Carbon B3NO2 Exotic Heterocycles: Synthesis,Dynamics, and Catalysis

The B₃NO₂ six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B₃NO₂ ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.     

Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Benzene fused five-membered heterocycles. A theoretical approach

The Nuclear Independent Chemical Shift of each ring, as a criterion of aromaticity, is used to explain the stability order of benzopyrrole, benzofuran and benzothiophene, and their isomers. The results indicate that the benzene ring is aromatic in all the systems. The five-membered rings of benzopyrrole, benzofuran and benzothiophene are also aromatic, whereas those of isobenzopyrrole, isobenzofuran and isobenzothiophene are non-aromatic. This could be an explanation of the stability of the former molecules. The molecular orbitals and the condensed Fukui functions derived from the electronic structure calculations are also reported. These reactivity indices explain the expected electrophilic substitution of these compounds. The theoretical structure, ionization energies, order of aromaticity, stability and reactivity are in good agreement with the experimental results. The usefulness of this approach to determine the reactivity is discussed since their stability and reactivity may be understood. The reactivity indices are useful to explain and confirm the experimental information, and for molecules with unknown reactive behavior, this approach could help to predict some of the reactions.