The Rivalry between Intramolecular Tetrel Bonds and Intermolecular Hydrogen Bonds in (O-Si) Chelates of N-Silylmethylamides and -ureas. A Theoretical Study.

The comparison of the results of theoretical calculations of (O-Si) chelates of N-silylmethylated amides and ureas with the axial chlorine or fluorine atom at silicon to the data of X-ray analysis of related compounds revealed the formation of covalent O-Si tetrel bonds (TB) or noncovalent O⋅⋅⋅Si tetrel bonds (NTB). The nature of the formed tetrel bond depends on the substituents at silicon and the polarity of the medium. The competition between the intramolecular TB and intermolecular hydrogen bonds (HB) with proton donors depends on the center of basicity involved in the formation of HB, which could be either oxygen or halogen. The hydrogen bonding can result in changing the nature of the tetrel bonds from covalent to noncovalent and vice versa by varying their lengths and energies. The O-Si bond energies estimated by QTAIM analysis of N-[(chlorodimethylsilyl)methyl]-N-methylacetamide and its H-complexes vary within the range of 7.2 and 12 kcal/mol in gas and solution, respectively, and correlate with the O-Si bond lengths.

The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact.

The reactions of alkenes with phenyl-N-triflylimino-λ3-iodane PhI=NTf (1) have been studied in different conditions. In methylene chloride, in the presence of N-halosuccinimides, the products of mono and bis-triflamidation were obtained. In MeCN, the product of bromotriflamidation (with NBS) with solvent interception or of bis-triflamidation (with NIS) is formed. The reaction with trans-stilbene in acetonitrile with NBS gave rise to cyclization to 2-methyl-4,5-diphenyl-1-triflyl-4,5-dihydro-1H-imidazole. In contrast, with NIS as an oxidant, both in CH2Cl2 and MeCN, the major product was 2,3-diphenyl-1-triflylaziridine formed in good yield. With NBS, aziridine is also formed but as a minor product, the major one being a mixture of diastereomers of the product of bromotriflamidation. The reaction of compound 1 with vinylcyclohexane in methylene chloride affords the mixtures of regioisomers of the products of halotriflamidation, whereas in acetonitrile, the products of solvent interception and cyclization to the imidazoline are formed. A mechanism explaining the formation of all isolated products is proposed.

Gas-Phase Structure of 3,7,9-tris(trifluoromethylsulfonyl)-3,7,9-triazabicyclo[3.3.1]nonane by GED and Theoretical Calculations.

The molecular structure and conformational and rotational composition of 3,7,9-tris(trifluoromethylsulfonyl)-3,7,9-triazabicyclo[3.3.1]nonane 1 have been investigated by synchronous gas-phase electron diffraction/mass spectrometry GED/MS and theoretical calculations (B3LYP and M06-2X with cc-pVTZ and aug-cc-pVTZ basis sets) and compared to the X-ray structure. All 16 possible conformers and rotamers were calculated, differing by the conformations of the two piperazine rings, orientation of the CF3 groups relative to these rings, and non-equivalence of the two wings of the butterfly structure. The optimized geometry of the most stable 1-c-out-2-c-out conformer coincides with that in the crystal. In contrast to only one conformer determined by X-ray, the GED analysis revealed the presence of five conformers, 1-c-out-2-c-out (I), 1-c-in-2-c-out (II), 1-c-out-2-c-in (III), 1-b-out-2-c-out (IV), 1-c-out-2-b-out (V) in the ratio of I:(II + III):IV:V = 36(10):42(6):22(10):0(10). The experimental results are better reproduced by calculations performed for 428 K (the temperature of the GED experiment) than for 298 K (standard), and most satisfactorily at the M06-2X/aug-cc-pVTZ level of theory.

2-Amino-1,3-benzothiazole: Endo N-Alkylation with α-Iodo Methyl Ketones Followed by Cyclization.

Reactions of 2-amino-1,3-benzothiazole with aliphatic, aromatic and heteroaromatic α-iodoketones in the absence of bases or catalysts have been studied. The reaction proceeds by N-alkylation of the endocyclic nitrogen atom followed by intramolecular dehydrative cyclization. The regioselectivity is explained and the mechanism of the reaction is proposed. A number of new linear and cyclic iodide and triiodide benzothiazolium salts have been obtained and their structure proved by NMR and UV spectroscopy.

A low-temperature dynamic 1 H, 13 C, and 77 Se NMR study of 2,2'-selenodicyclohexanol.

2,2'-Selenodicyclohexanol 1 was shown to exist as two (all-trans-achiral and all-trans-chiral) stereoisomers with all C-Se and C-OH bonds in equatorial orientations. When the temperature is lowered, the 1 H, 13 C, and 77 Se NMR spectra exhibit a strongly one-sided dynamic process, which involves sterically hindered rotation about the C-Se bond. Structures, free energy differences of the rotamers ΔG°, and the rotational barrier were determined and confirmed by quantum chemical calculations at the M06-2X/6-311++G**, M06-2X/cc-pVTZ, and MP2/6-311+G** levels of theory.

Conjugative Stabilization versus Anchimeric Assistance in Carbocations.

In this study, an old concept of anchimeric assistance is viewed from a different angle. Primary cations with two different heteroatomic substituents in the α-position to the cationic carbon atom CHXY−CH2+ (X, Y = Me2N, MeO, Me3Si, Me2P, MeS, MeS, Br) can be stabilized by the migration of either the X or Y group to the cation center. In each case, the migration can be either complete, resulting in the transfer of the migrating group to the adjacent carbon atom and the formation of a secondary carbocation stabilized by the remaining heteroatom, or incomplete, leading to an anchimerically assisted iranium ion. For all combinations of the above groups, these transformations have been studied by theoretical analysis at the MP2/aug-cc-pVTZ level and were shown to occur depending on the ability of anchimeric assistance by X and Y, as well as the conformation of the starting primary carbocation. In the conformers of α-amino cations with the p-orbital, C−N bond and the nitrogen lone pair in one plane, the Me2N group migrates to the cationic center to give aziranium ions. Otherwise, the second heteroatom is shifted to give iminium ions, without or with very slight anchimeric assistance. In the α-methoxy cations, the MeO group can be shifted to the cationic center to give the O-anchimerically assisted ions as local minima, the global minima being the ions anchimerically assisted by another heteroatom. The electropositive silicon tends to migrate towards the cationic center, but with the formation of a π-complex of the Me3Si cation with the C=C bond rather than a Si-anchimerically assisted cation. The phosphorus atom can either fully migrate to the cationic center (X = P, Y = S, Se) or form anchimerically stabilized phosphiranium ions (X = P, Y = O, Si, Br). The order of the anchimeric assistance for the heaviest atoms decreases in the order Se >> S > Br.

Iodine-Mediated Alkoxyselenylation of Alkenes and Dienes with Elemental Selenium.

A one-pot synthesis of linear and cyclic ß-alkoxyselenides is developed through the iodine-mediated three-component reaction of elemental selenium with alkenes (dienes) and alcohols. Selenylation of 1,5-hexadiene gives 2,5-di(methoxymethyl)tetrahydroselenophene and 2-methoxy-6-(methoxymethyl)tetrahydro-2H-selenopyran via the 5-exo-trig and 6-endo-trig cyclization. 1,7-Octadiene affords only linear 1:2 adduct with two terminal double bonds. 1,5-Cyclooctadiene results in one diastereomer of 2,6-dialkoxy-9-selenabicyclo [3.3.1]nonanes via 6-exo-trig cyclization. With 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane, the first ring-substituted representative of a very rare class of heterocycles, 1,4,2,6-oxaselenadisilinanes, was obtained at a high yield.

Synthetic Approaches to Biologically Active C-2-Substituted Benzothiazoles.

Numerous benzothiazole derivatives are used in organic synthesis, in various industrial and consumer products, and in drugs, with a wide spectrum of biological activity. As the properties of the benzothiazole moiety are strongly affected by the nature and position of substitutions, in this review, covering the literature from 2016, we focus on C-2-substituted benzothiazoles, including the methods of their synthesis, structural modification, reaction mechanisms, and possible pharmacological activity. The synthetic approaches to these heterocycles include both traditional multistep reactions and one-pot atom economy processes using green chemistry principles and easily available reagents. Special attention is paid to the methods of the thiazole ring closure and chemical modification by the introduction of pharmacophore groups.

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization.

Allyl halides with triflamide under oxidative conditions form halogen-substituted amidines. Allyl cyanide reacts with triflamide in acetonitrile or THF solutions in the presence of NBS to give the products of bromotriflamidation with a solvent interception, whereas in CH2Cl2 two regioisomers of the bromotriflamidation product without a solvent interception were obtained. The formed products undergo base-induced dehydrobromination to give linear isomers with the new C=C bond conjugated either with the nitrile group or the amidine moiety or alkoxy group. Under the same conditions, the reaction of allyl alcohol with triflamide gives rise to amidine, which was prepared earlier by the reaction of diallyl formal with triflamide. Unlike their iodo-substituted analogs, bromo-substituted amidines successfully transform into imidazolidines under the action of potassium carbonate.

Modern Approaches to the Synthesis and Transformations of Practically Valuable Benzothiazole Derivatives.

The review is devoted to modern trends in the chemistry of 2-amino and 2-mercapto substituted benzothiazoles covering the literature since 2015. The reviewed heterocycles belong to biologically active and industrially demanded compounds. Newly developed synthesis methods can be divided into conventional multistep processes and one-pot, atom economy procedures, realized using green chemistry principles and simple reagents. The easy functionalization of the 2-NH2 and 2-SH groups and the benzene ring of the benzothiazole moiety allows considering them as highly reactive building blocks for organic and organoelement synthesis, including the synthesis of pharmacologically active heterocycles. The review provides a summary of findings, which may be useful for developing new drugs and materials and new synthetic approaches and patterns of reactivity.

Silacyclohexanes, Sila(hetero)cyclohexanes and Related Compounds: Structure and Conformational Analysis.

Conformational analysis of Si-mono- and Si,Si-disubstituted silacyclohexanes as well as their analogues with a heteroatom(s) in the ring is reviewed with the focus on the recent results. Experimental measurements in the gas phase (gas electron diffraction, GED) and low temperature NMR spectroscopy (LT NMR) on 1H, 13C and 29Si nuclei are described along with theoretical calculations at the DFT and MP2 levels of theory. Structural and conformational specific features are shown to be principally different from those of the carbon predecessors - the corresponding cyclohexanes, oxanes, thianes and piperidines. The role of various effects (steric, hyperconjugation, stereoelectronic, electrostatic) is demonstrated.

Structural and Conformational Aspects in the Chemistry of Heterocycles.

Heterocyclic compounds represent more than half of all known organic compounds, so the growing interest in this field of chemistry is not surprising [...].

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study.

A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene-sulfonamide in the presence of oxidative system (ButOCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and p-nosylamide were taken as the reagents. ButOI generated from ButOCl and NaI reacts with sulfonamides to give N-iodinated sulfonamides RSO2NHI and RSO2NI2 as active intermediates, the iodinating activity of the latter being notably higher. The analysis allowed to answer such challenging questions as different reactivity of nonfluorinated sulfonamides leading to aziridination and of triflamide resulting in the formation the main products of bis-triflamidation, or different regioselectivity of halogenation of styrene and trimethyl(vinyl)silane caused by a linear intermediate iodonium cation in the former case and a cyclic one in the latter.

2H-Indazole Tautomers Stabilized by Intra- and Intermolecular Hydrogen Bonds.

2-[(2H-Indazol-3-yl)methylene]-1H-indene-1,3(2H)-dione 6 and (E)-2-[(2H-indazol-3-yl)methylene]-2,3-dihydro-1H-inden-1-one 7 have been synthesized. In the crystal, the NH hydrogen atom of 6 is disordered between the N(1) and N(2) atoms with the population ratio of 0.69:0.31. Molecule 7 crystallizes in two tautomeric polymorphs: 7-1H tautomer (yellow) and 7-2H tautomer (red). Both 6 and 7 form centrosymmetric dimers in the crystal with the monomeric units linked by C═O···H···N bifurcated hydrogen bonds in 6 and N-H···N hydrogen bonds in 7. According to 1H and 13C NMR data, in DMSO-d6 solution, the 6-1H tautomer predominates, whereas in less polar CDCl3 or CD2Cl2, the 6-2H tautomer is stabilized by a strong N-H···O═C intramolecular hydrogen bond. Compound 7 in dimethyl sulfoxide (DMSO) or ethanol solutions exists in the form of 7-1H and 7-2H tautomers. On the example of the 7-2H tautomer, it was shown for the first time that the 2H tautomers of 3-substituted indazoles can be stabilized by an intermolecular hydrogen bond and may remain in aprotic solvents almost indefinitely. However, in the open air or in water, fast 2H → 1H tautomerization occurs. As follows from density functional theory calculations, the high stability of the 2H form in solution is due to the formation of centrosymmetric dimers, which are more stable than the corresponding dimers of the 1H tautomer.

Solvent interception, heterocyclization and desilylation upon NBS-induced sulfamidation of trimethyl(vinyl)silane.

The reaction of trimethyl(vinyl)silane with sulfonamides in the presence of N-bromosuccinimide was shown to proceed regioselectively in methylene chloride under mild conditions and led to the products of bromosulfamidation in up to 88% yield. The obtained adducts undergo base-promoted dehydrobromination to give 2-trimethylsilyl-N-sulfonyl aziridines in a close to quantitative yield. In the reaction with trifluoromethanesulfonamide in acetonitrile or tetrahydrofuran, the Ritter-type (solvent-interception) products were obtained and converted to 1-triflyl-2-methyl-5-(trimethylsilyl)-2-imidazoline or 4-triflyl-3-(trimethylsilyl)-1,4-oxazocane in almost quantitative yield.

Tetrel Bonding along the Pathways of Transsilylation and Alkylation of N-Trimethylsilyl- N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes.

A quantum chemical study has been carried out on the complexes formed in the first stage of the reaction of (chloromethyl)trifluorosilane with an ambident nucleophile, N-trimethylsilyl- N-methylacetamide, existing in the amide and imidate tautomeric forms. The analysis of molecular electrostatic potential maps of the electrophile molecule revealed the presence of two σ-holes belonging to the Si and C atoms. Each of the two tautomers of the nucleophile form complexes having O···Si, O···C, N···Si, and N···C bonds of different characters. The natural bond orbital and quantum theory of atoms in molecules analyses showed the presence of the O···Si and O···C tetrel bonds or of electrostatic interaction in the complexes with the amide tautomer, depending on the orientation of the components. The imidate tautomer forms a complex with covalent N-Si bond, whereas the N···C bond is very weak. The effect of silicon atom arrangement on the structure of complexes between N-trimethylsilyl- N-methylacetamide and bifunctional silanes ClCH2SiX nF3- n (X = Me, OMe, Cl, n = 1, 2) and the effect of σ-hole tetrel bonding interactions on the reaction pathways are discussed.

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature 13C NMR Spectroscopy and Theoretical Calculations.

New Si-phenyl-substituted silacyclohexanes and 3-silatetrahydropyrans have been synthesized and studied with respect to the conformational equilibria of the heterosix-membered ring by low temperature 13C NMR spectroscopy and quantum chemical calculations. For 1-methoxy-1-phenylsilacyclohexane 1 and 3-phenyl-3-silatetrahydropyran 4 the conformational equilibria could be frozen and assigned. The Phax ⇆ Pheq equilibrium constants at 103 K are 2.21 for 1 and 4.59 for 4. In complete agreement with former studies of similar silicon compounds, molecules 1 and 4 prefer to adopt the Pheq conformation. The conformational equilibria of 1-hydroxy-1-phenylsilacyclohexane 2 and 3-hydroxy-3-phenyl-3-silatetrahydropyran 3 could not be frozen at 100 K and proved to be heavily one-sided (if not anancomeric). Obviously, there is a general trend of predominance of Phax conformer in the gas phase and of Pheq in solution. For the isolated molecules of silanols 2 and 3, calculations allowed to explain the axial predominance of the phenyl group by a larger polarization of the Si-Ph than of the Si-O bond in the Phax conformer and additional destabilization of 3-Pheq conformer by repulsion of unidirectional dipoles of the endocyclic oxygen lone pair and of the highly polar axial Si-O bond.

Photoinduced Intramolecular Bifurcate Hydrogen Bond: Unusual Mutual Influence of the Components.

A series of 7-hydroxy-2-methylidene-2,3-dihydro-1H-inden-1-ones with 2-pyrrolyl (3), 4-dimethylaminophenyl (4), 4-nitrophenyl (5), and carboxyl group (6) as substituents at the exocyclic double bond was synthesized in the form of the E-isomers (4-6) or predominantly as the Z-isomer (3) which in solution is converted to the E-isomer. The synthesized compounds and their model analogues were studied by NMR spectroscopy, X-ray analysis, and MP2 theoretical calculations. The E-isomers having intramolecular O-H···O═C hydrogen bond are converted by UV irradiation to the Z-isomers having bifurcated O-H···O···H-X hydrogen bond. Unexpected shortening (and, thus, strengthening) of the O-H···O═C component of the bifurcated hydrogen bond upon the formation of the C═O···H-X hydrogen bond was found experimentally, proved theoretically (MP2), and explained by a roundabout interaction of the H-donor (HX) and H-acceptor (C═O) via the system of conjugated bonds.

Molecular Structure and Conformational Analysis of 1-Phenyl-1-X-1-Silacyclohexanes (X = F, Cl) by Electron Diffraction, Low-Temperature NMR, and Quantum Chemical Calculations.

The molecular structure and conformational preferences of 1-phenyl-1-X-1-silacyclohexanes C5H10Si(Ph,X) (X = F (3), Cl (4)) were studied by gas-phase electron diffraction, low-temperature NMR spectroscopy, and high-level quantum chemical calculations. In the gas phase only three (3) and two (4) stable conformers differing in the axial or equatorial location of the phenyl group and the angle of rotation about the Si-CPh bond (axi and axo denote the Ph group lying in or out of the X-Si-CPh plane) contribute to the equilibrium. In 3 the ratio Pheq:Phaxo:Phaxi is 40(12):55(24):5 and 64:20:16 by experiment and theory, respectively. In 4 the ratio Pheq:Phaxo is 79(15):21(15) and 71:29 by experiment and theory (M06-2X calculations), respectively. The gas-phase electron diffraction parameters are in good agreement with those obtained from theory at the M06-2X/aug-ccPVTZ and MP2/aug-cc-pVTZ levels. Unlike the case for M06-2X, MP2 calculations indicate that 3-Pheq conformer lies 0.5 kcal/mol higher than the 3-Phaxo conformer. As follows from QTAIM analysis, the phenyl group is more stable when it is located in the axial position but produces destabilization of the silacyclohexane ring. By low-temperature NMR spectroscopy the six-membered-ring interconversion could be frozen at 103 K and the present conformational equilibria of 3 and 4 could be determined. The ratio of the conformers is 3-Pheq:3-Phax = (75-77):(23-25) and 4-Pheq:4-Phax = 82:18.

Synthesis and Conformational Analysis of 3-Methyl-3-silatetrahydropyran by GED, FTIR, NMR, and Theoretical Calculations: Comparative Analysis of 1-Hetero-3-methyl-3-silacyclohexanes.

3-Methyl-3-silatetrahydropyran 1 was synthesized and its molecular structure and conformational behavior was studied by gas-phase electron diffraction (GED), FTIR, low temperature (1)H and (13)C NMR spectroscopy, and by theoretical calculations (DFT, MP2). Two conformers, 1-ax and 1-eq, were located on the potential energy surface. In the gas phase, a slight predominance of the axial conformer was determined, with the ratio 1-ax:1-eq = 54(9):46(9) (from GED) or 53:47 or 61:39 (from IR). In solution, LT NMR spectroscopy at 103 K gives the ratio 1-ax:1-eq = 35:65 (-ΔG°103 = 0.13 kcal/mol). Simulation of solvent effects using the PCM continuum model or by calculation of the corresponding solvent-solute complexes allowed us to rationalize the experimentally observed opposite conformational predominance of the conformers of 3-methyl-3-silatetrahydropyran in the gas phase and in solution. Comparative analysis of the effect of heteroatom in 1-hetero-3-methyl-3-silacyclohexanes on the structure, stereoelectronic interactions, and relative energies of the conformers is done.