RESUMEN
Aminated nitrogen heterocycles are valuable motifs across numerous chemical industries, perhaps most notably in small molecule drug discovery. While numerous strategies for installing nitrogen atoms onto azaarenes exist, most require prefunctionalization and methods for direct C-H amination are almost entirely limited to position C2. Herein, we report a method for the direct C2 and C4 C-H amination of fused azaarenes via in situ activation with a bispyridine-ligated I(III) reagent, [(Py)2IPh]2OTf, or Py-HVI. Unlike commonly used N-oxide chemistry, the method requires no preoxidation of the azaarene and provides unprecedented direct access to C4 amination products. The resulting N-heterocyclic pyridinium salts can be isolated via simple trituration. The free amine can be liberated under mild Zincke aminolysis, or the amination and cleavage can be telescoped to a one-pot process. The scope of the method is broad; the conditions are mild and operationally simple, and the aminated products are produced in good to excellent yields. Computational studies provide insights into the mechanism of activation, which involves an unusual direct nucleophilic functionalization of an I(III) ligand, as well as a kinetic basis for the observed C2 and C4 amination products.
RESUMEN
The synthesis and structural characterization of an electron poor Au(III) trication bearing 2 imidazole and 2 acetonitrile ligands is described. The new complex is capable of aryl C-H metalation with the formation of a monomesitylene complex and also demonstrated to be highly oxidizing in the rapid room temperature conversion of cyclohexene to benzene.
RESUMEN
Hypervalent iodine(iii) compounds of the general structure ArIL2 are widely used as oxidizing agents for a variety of applications across both organic and inorganic chemistry. Considerable work has been done on the activation of these compounds by tuning the ligands at the iodine centre. This perspective summarises the work of our and other groups on rectification of historically misidentified iodine(iii) reagents of this class, and the syntheses of activated species. Recent advances focusing on increasing the oxidative capacity of I(iii) moieties using Lewis and Brønsted acids and Lewis bases as well as the activation of halogens with I(iii) are discussed.
RESUMEN
Bis(1-methyl-ortho-carboranyl)borane (HBMeoCb2) is a very strong Lewis acid that reacts with the isolated silanols present on silica partially dehydroxylated at 700 °C (SiO2-700) to form the well-defined Lewis site MeoCb2B(OSi≡) (1) and H2. 11B{1H} magic-angle spinning (MAS) nuclear magnetic resonance (NMR) data of 1 are consistent with that of a three-coordinate boron site. Contacting 1 with OâPEt3 (triethylphosphine oxide TEPO) and measuring 31P{1H} MAS NMR spectra show that 1 preserves the strong Lewis acidity of HBMeoCb2. Hydride ion affinity and fluoride ion affinity calculations using small molecules analogs of 1 also support the strong Lewis acidity of the boron sites in this material. Reactions of 1 with Cp2Hf(13CH3)2 show that the Lewis sites are capable of abstracting methide groups from Hf to form [Cp2Hf-13CH3][H313C-B(MeoCb2)OSi≡], but with a low overall efficiency.
RESUMEN
The borylation of aryl substituted pyridines is an effective way of preparing B-N doped conjugated organic frameworks. Trihaloborane Lewis acids are often employed for this protocol, and may require further functionalization to replace the remaining halides on boron. We report a new, fully characterized, electrophilic borylating agent, (C6F5)2B(κ2-NTf2), that smoothly incorporates a -B(C6F5)2 unit into the model substrate 2-phenylpyridine. To demonstrate its utility in preparing more complex B-N doped structures, we use it to prepare seven examples of the 6a,13a-diaza-7,14-dibora-dibenzo[a,h]pyrene framework, with substituents of varying donor properties. The structural, redox, and photophysical properties of this new family of B-N doped polycyclic hydrocarbon compounds were probed experimentally and computationally.
RESUMEN
In pursuit of a genuine bromo-λ3-iodane, it has been found that the combination of Br2 and electron deficient λ3-iodanes can result in the delivery of both bromine atoms from Br2 to a range of aryl substrates, some highly deactivated. These brominations occur rapidly in common chlorinated solvents at room temperature and can be achieved with the catalytic activation of commercially available PhI(OAc)2 and PhI(OTFA)2. para-NO2 substituted derivatives are employed to direct bromination towards more deactivated substrates. The mechanism of Br2 activation is discussed with insights being made, however it remains unclear.
RESUMEN
Synthesis and crystallographic characterization of NO2-C6H4-I(NTf2)2 (NTf2 = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions that ArI(OTf)2 is unable to and theoretical analysis indicates Ar-I(NTf2)2 is the most oxidizing in the ArIL2 class of compounds known and may also be the most oxidizing compound in the class practically possible.
RESUMEN
The recently discovered I(III) reagent NO2-C6H4-I(OTf)2 is found to rapidly react with hydride sources, including HSiEt3 and relatively hydridic C-H precursors. These represent the first distinct reactions involving direct hydride abstraction by I(III) under ambient conditions. Direct C-F abstraction is also demonstrated, as well as oxidation of cyclic alkenes to aromatic rings, all representing new reactions for I(III) demonstrating the very high reactivity of NO2-C6H4-I(OTf)2.
RESUMEN
The Lewis acidity of primary, secondary, and tertiary boranes with phenyl, pentafluorophenyl, and all three isomers of the C-substituted icosahedral carboranes (ortho, meta, and para) was investigated by computing their fluoride, hydride, and ammonia affinities as well as their global electrophilicity indices and LUMO energies. From these calculations, it was determined that the substituent effects on the Lewis acidity of these boranes follow the trend of ortho-carborane > meta-carborane > para-carborane > C6F5 > C6H5.
RESUMEN
The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via oxidation of pyridine giving a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides.
RESUMEN
A stable organometallic compound with a Be-Be bond has been synthesized.
RESUMEN
The Lewis superacid, bis(1-methyl-ortho-carboranyl)borane, is rapidly accessed in two steps. It is a very effective hydroboration reagent capable of B-H addition to alkenes, alkynes, and cyclopropanes. To date, this is the first identified Lewis superacidic secondary borane and most reactive neutral hydroboration reagent.
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The first crystallographic characterization of chloronium cations stabilized by pyridine ligands (P. Pröhm, W. Berg, S. M. Rupf, C. Müller and S. Riedel, Chem. Sci., 2023, https://doi.org/10.1039/D2SC06757A) is discussed in the context of coordination chemistry at chlorine.
RESUMEN
Both mixed λ3-iodoarenes and λ3-iodoarenes possessing -OTf ligands are coveted for their enhanced reactivities. Here we describe the synthesis, reactivity, and comprehensive characterisation of two new ArI(OTf)(X) species, a class of compound that were previously only invoked as reactive intermediates where X = Cl, F and their divergent reactivity with aryl substrates. A new catalytic system for electrophilic chlorination of deactivated arenes using Cl2 as the chlorine source and ArI/HOTf as the catalyst is also described.
RESUMEN
The looming threat of a "post-antibiotic era" has been caused by a rapid rise in antibacterial resistance and subsequent depletion of effective antibiotic agents in the clinic. An efficient strategy to address this shortfall lies in the reengineering of pre-existing and commercially available antibiotic drugs. This is exemplified by dimerization, a design concept in which two pharmacophores are covalently linked to form a new chemical entity. The cage hydrocarbons cubane (1), bicyclo[2.2.2]octane (BCO) (2), adamantane (3), and bicyclo[1.1.1]pentane (BCP) (4) present themselves as an attractive family of linkers in this regard. In this report, all four hydrocarbon cages were employed as linkers in a series of dimers based on the commercially available antibiotics trimethoprim and tedizolid. A detailed synthetic roadmap for the protection and deprotection of each pharmacophore is outlined. Several members of the trimethoprim series showed activity on par with that of their trimethoprim progenitor, although this was not the case for the tedizolid series. The design strategy outlined herein highlights the utility of the group as a platform for the rapid and modular construction of future novel antibiotics.
Asunto(s)
Oxazolidinonas , Trimetoprim , Trimetoprim/farmacología , Antibacterianos/farmacología , Antibacterianos/uso terapéutico , HidrocarburosRESUMEN
PhIBr2, first purported to exist over 100 years ago, has been subject of few reports due to its low stability. However, a recent publication proposes a reaction of PIFA (PhI(OC(O)-CF3)2) with TMSBr to form PhIBr2in situ and demonstrated its efficacy in aryl brominations. This report investigates this synthesis by replicating bromination reactions claiming to use in situ PhIBr2 as described. The spectroscopical and computational results indicate formation of PhI and Br2 where Br2 is responsible for bromination and no supporting evidence for invoking PhIBr2 as an intermediate is found.
Asunto(s)
HalogenaciónRESUMEN
The synthesis of tris(ortho-carboranyl)borane (BoCb3 ), a single site neutral Lewis superacid, in one pot from commercially available materials is achieved. The high fluoride ion affinity (FIA) confirms its classification as a Lewis superacid and the Gutmann-Beckett method as well as adducts with Lewis bases indicate stronger Lewis acidity over the widely used fluorinated aryl boranes. The electron withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO rationalize the unusually high Lewis acidity. Catalytic studies indicate that BoCb3 is a superior catalyst for promoting C-F bond functionalization reactions than tris(pentafluorophenyl)borane [B(C6 F5 )3 ].
RESUMEN
PhI(OTf)2 and related ArI(OTf)2 species have been incorrectly invoked as intermediates in oxidation reactions for many years. We recently established that such compounds did not yet exist but remain an attractive target. Here we describe the synthesis, isolation, and structural characterization of NO2 -PhI(OTf)2, which is resistant to decomposition and more reactive than PhI(OTf)(OAc), the species previously misidentified as PhI(OTf)2 .
Asunto(s)
Dióxido de Nitrógeno , Oxidación-ReducciónRESUMEN
Based on statistical analysis of CHN combustion results of 18 international service providers, it is determined that the ±0.4% deviation most commonly required by chemistry journals is not justified.
RESUMEN
A study on the kinetics of the activation of PhICl2 using catalytic chloride or pyridine in electrophilic chlorination of arenes has been carried out. The results indicate that both catalysts induce the release of Cl2 from PhICl2 and that the Cl2 is the active reagent for chlorination in these reactions.