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A green one-pot 2,3,6-trifunctionalization of N-alkyl/aryl indoles was achieved by adding three equivalents of N-Br sulfoximine to the indole solution. A variety of 2-sulfoximidoyl-3,6-dibromo indoles were prepared with 38–94% yields using N-Br sulfoximines as both brominating and sulfoximinating reagents. Based on the results of controlled experiments, we propose that a radical substitution involving 3,6-dibromination and 2-sulfoximination occurs in the reaction process. This is first time that 2,3,6-trifunctionalization of indole in one pot has been achieved.

Fluorochemistry is a field of tremendous developments and advances in several areas of science including materials, pharmaceuticals and agriculture. This makes the design and synthesis of fluorine-containing substances highly desirable research targets. The sub-area of synthetic perfluorinated chemistry proportionately attracts widespread interest by applying to all areas of chemistry including organic and inorganic. Particularly, the latter is much underdeveloped as metal complexes with perfluoroalkyl moieties are scarce, with the vast majority of perfluorinated analogs, of long known, halo and alkylated derivatives never having been synthesized. Focusing on the chemistry of trifluoromethyl group, which is the most important in the class of perfluoroalkyls, we set out to explore the possibility of synthesizing and completely characterizing a cyclohexadienyl metal complex. Upon utilizing a number of trifluorometylating reagents, we only arrived at an efficient preparation by the use of Morrison’s trifluormethylating reagent. As a result, the new, air- and moisture-sensitive complex (η[sup.5]-C[sub.6]H[sub.7])Fe(CO)[sub.2]CF[sub.3], was prepared in 71% yield, using a nucleophilic iodo-for-trifluoromethyl substitution, and was completely characterized including by X-ray crystallography.

The efficient “One-pot” CuCl[sub.2]-catalyzed C–S bond coupling reactions were developed for the synthesis of dibenzo[b,f][1,4]thiazepines and 11-methy-ldibenzo[b,f][1,4]thiazepines via 2-iodobenzaldehydes/2-iodoacetophenones with 2-aminobenzenethiols/2,2′-disulfanediyldianilines by using bifunctional-reagent N, N′-dimethylethane-1,2-diamine (DMEDA), which worked as ligand and reductant. The reactions were compatible with a range of substrates to give the corresponding products in moderate to excellent yields.

A spherical amide with C [sub.3] symmetry was synthesized by a one-step cyclization reaction using triphenylphosphine and hexachloroethane as coupling reagents. This method enabled synthesis of N-benzyl and N-allyl derivatives, which could not be obtained by the previously reported method. The optical resolution of each compound was measured, and their electronic circular dichroism spectra revealed that they were mirror images. The high structural symmetry resulted in a higher Δε (molar absorption difference against right or left circular polarization: εL − εR value compared to that of another structural isomer synthesized previously. The absolute structure of the enantiopure crystal of the N-benzyl derivative was determined using the Flack parameter obtained by X-ray crystallographic analysis.

We investigate the possibility of modification of SnS[sub.2] powder through sonochemical synthesis with the addition of an organic ligand. For that purpose, two organic dyes are used, Phenol Red and Anthraquinone Violet. All obtained powders are characterized using XRD, SEM, EDX, FT-IR, and UV-Vis investigations. Synthesized samples showed composition and structural properties typical for sonochemically synthesized SnS[sub.2]. However, investigation with the Tauc method revealed that SnS[sub.2] powder modified with Phenol Red exhibits a significant shift in value of optical bandgap to 2.56 eV, while unmodified SnS[sub.2] shows an optical bandgap value of 2.42 eV. The modification of SnS[sub.2] powder with Anthraquinone Violet was unsuccessful. The obtained nanopowders were utilized as photocatalysts in the process of Metanil Yellow degradation, revealing that SnS[sub.2] modified with Phenol Red shows about 23% better performance than the unmodified one. The mean sonochemical efficiency of the performed synthesis is also estimated as 9.35 µg/W.

meso-Tetrahexylporphyrin was converted to its corresponding 7,8-dihydroxychlorin using an osmium tetroxide-mediated dihydroxylation strategy. Its diol moiety was shown to be able to undergo a number of subsequent oxidation reactions to form a chlorin dione and porpholactone, the first meso-alkylporphyrin-based porphyrinoid containing a non-pyrrolic building block. Further, the diol chlorin was shown to be susceptible to dehydration, forming the porphyrin enol that is in equilibrium with its keto-chlorin form. The meso-hexylchlorin dione could be reduced and it underwent mono- and bis-methylation reactions using methyl-Grignard reagents, and trifluoromethylation using the Ruppert-Prakash reagent. The optical and spectroscopic properties of the products are discussed and contrasted to their corresponding meso-aryl derivatives (where known). This contribution establishes meso-tetrahexyl-7,8-dihydroxychlorins as a new and versatile class of chlorins that is susceptible to a broad range of conversions to generate functionalized chlorins and a pyrrole-modified chlorin analogue.

Due to boron’s metalloid properties, aromatic boron reagents are prevalent synthetic intermediates. The direct borylation of aryl C-H bonds for producing aromatic boron compounds offers an appealing, one-step solution. Despite significant advances in this field, achieving regioselective aryl C-H bond borylation using simple and readily available starting materials still remains a challenge. In this work, we attempted to enhance the reactivity of the electron-donor-acceptor (EDA) complex by selecting different bases to replace the organic base (NEt[sub.3]) used in our previous research. To our delight, when using NH[sub.4]HCO[sub.3] as the base, we have achieved a mild visible-light-mediated aromatic C-H bond borylation reaction with exceptional regioselectivity (rr > 40:1 to single isomers). Compared with our previous borylation methodologies, this protocol provides a more efficient and broader scope for aryl C-H bond borylation through the use of N-Bromosuccinimide. The protocol’s good functional-group tolerance and excellent regioselectivity enable the functionalization of a variety of biologically relevant compounds and novel cascade transformations. Mechanistic experiments and theoretical calculations conducted in this study have indicated that, for certain arenes, the aryl C-H bond borylation might proceed through a new reaction mechanism, which involves the formation of a novel transient EDA complex.

In this work, we studied lead(II) and cobalt(II) complexation of derivatives [2-B[sub.10]H[sub.9]O(CH[sub.2])[sub.2]O(CH[sub.2])[sub.2]N[sub.3]][sup.2−] and [2-B[sub.10]H[sub.9]O(CH[sub.2])[sub.5]N[sub.3]][sup.2−] of the closo-decaborate anion containing pendant azido groups in the presence of 1,10-phenanthroline and 2,2′-bipyridyl. Mononuclear [PbL[sub.2]An] and binuclear [Pb[sub.2]L[sub.4](NO[sub.3])[sub.2]An] lead complexes (where An is the N[sub.3]-substituted boron cluster) were isolated and studied by IR spectroscopy and elemental analysis. The mononuclear lead(II) complex [Pb(phen)[sub.2][B[sub.10]H[sub.9]O(CH[sub.2])[sub.2]O(CH[sub.2])[sub.2]N[sub.3]] and the binuclear lead(II) complex [Pb[sub.2](phen)[sub.4](NO[sub.3])[sub.2][B[sub.10]H[sub.9]O(CH[sub.2])[sub.5])N[sub.3]] were determined by single-crystal X-ray diffraction. In complex [Pb[sub.2](phen)[sub.4](NO[sub.3])[sub.2][B[sub.10]H[sub.9]O(CH[sub.2])[sub.5])N[sub.3]], the boron cluster is coordinated by the metal atom only via the 3c2e MHB bonds. In complex [Pb(phen)[sub.2][B[sub.10]H[sub.9]O(CH[sub.2])[sub.2]O(CH[sub.2])[sub.2]N[sub.3]], the coordination environment of the metal includes BH groups of the boron cluster and the oxygen atom of the exo-polyhedral substituent. When the reaction was performed in a CH[sub.3]CN/water mixture, the binuclear lead(II) complex [(Pb(bipy)NO[sub.3])(Pb(bipy)[sub.2]NO[sub.3])(B[sub.10]H[sub.9]O(CH[sub.2])[sub.2]O(CH[sub.2])[sub.2]N[sub.3])]·CH[sub.3]CN·H[sub.2]O was isolated, where the boron cluster acts as a bridging ligand between lead atoms coordinated by the boron cage via the O atoms of the substituent and/or the BH groups. In the course of cobalt(II) complexation, the starting compound (Ph[sub.4]P)[sub.2][B[sub.10]H[sub.9]O(CH[sub.2])[sub.5]N[sub.3]] was isolated and its structure was also determined by X-ray diffraction. Although a number of lead(II) complexes with coordinated N[sub.3] are known from the literature, no complexes with the boron cluster coordinated by the pendant N[sub.3] group involved in the metal coordination have been isolated.

This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr[sub.3]-C[sub.6]H[sub.2]) with trimethylsilyl azide afforded the silyltriazene TripN[sub.2]N(SiMe[sub.3])[sub.2] in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH[sub.2] in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip[sub.2]-C[sub.6]H[sub.3]) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe[sub.3])Li in parallel, which afforded TerN(SiMe[sub.3])H after workup, and can be deprotected under acidic conditions to form the aniline TerNH[sub.2]. TripNH[sub.2] was furthermore converted to the sterically demanding β-diketimines [sup.RTrip]nacnacH (=HCRCN(Trip)[sub.2]H), with R = Me, Et and iPr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [([sup.iPrTrip]nacnac)MgH[sub.2]], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties.

Among phosphorylated derivatives, phosphinates occupy a prominent place due to their ability to be bioisosteres of phosphates and carboxylates. These properties imply the necessity to develop efficient methodologies leading to phosphinate scaffolds. In recent years, our team has explored the nucleophilic potential of silylated phosphonite towards various electrophiles. In this paper, we propose to extend our study to other electrophiles. We describe here the implementation of a cascade reaction between (trimethylsilyl)imidates and hypophosphorous acid mediated by a Lewis acid allowing the synthesis of aminomethylenebisphosphinate derivatives. The present study focuses on methodological development including a careful NMR monitoring of the cascade reaction. The optimized conditions were successfully applied to various aliphatic and aromatic substituted (trimethylsilyl)imidates, leading to the corresponding AMBPi in moderate to good yields.