Mass spectra of sterically crowded trialkylsilyl derivatives of nucleosides

The electron impact mass spectra of tert-butyldimethylsilyl-, cyclo-tetramethylene-tert-butylsilyl and cyclo-tetramethylene-isopropylsilyl- ether derivatives of ribo- and 2′-deoxyribonucleosides are described in detail. The interpretation of fragmentation pathways of full and mixed derivatives was aided by metastable ion decomposition studies, precise mass and deuterium labelling measurements, and spectra of mixed derivatives containing the ‘passive’ (in these spectra) trimethylsilyl group. The sterically crowded silyl groups have a powerful fragmentation directing effect. Elimination of a bulky radical, R˙ (tert-butyl or isopropyl), from the molecular ion produces the siliconium ion [M? R]⁺, which is the precursor for most of the other prominent ions in the spectra. These arise from ‘siliconium ion rearrangements’ resulting from the interaction of the positively charged siliconium ion center with electron dense regions (i.e. oxygens) in the molecule, to form cyclic silyloxonium ions which subsequently decompose. Since the interacting oxygen and silicon must be sterically accessible, the fragment ion types and their abundances are very dependent upon structure. Consequently, [M? R]⁺ ions formed from 2′, 3′ or 5′-O-silyl groups give rise to different sets of daughter ions which, for the most part, are not found, or have very low abundances, in the mass spectra of underivatized or trimethylsilylated nucleosides. Detailed information on sugar and base moieties and isomeric substitution is readily obtained.     

Stable simple enols. Self-catalyzed E/Z-isomerization of the sterically crowded 2-(m-methoxymesityl)-1,2-dimesitylethenol

(E)-2-(m-methoxymesityl)-1,2-dimesitylethenol (3a) isomerizes in the absence of a catalyst in solution to a 1.0:0.9 E/Z (3a/3b) equilibrium mixture. In CDCl3 the isomerization is first order in 3a within a run, but the plot of the rate constant k(obs) vs the changing [3a]0 in different runs is a half-parabola, indicating self-catalysis by more than one enol molecule. At 0.09 M enol, the isotope effect k(3a)/k(3a)-OD = 2.1. In the presence of 0.025-0.25 M pyridine-d5, the k(obs) vs [pyridine-d5] plot displays a bell-shaped profile. The change in the shape of the OH signals of the 3a/3b mixture at 295-430 K in C6D5NO2 was followed by DNMR. The four signals of the diastereomeric 3a/3b mixture observed at 330 K coalesce at 350 K with barriers of 18.3 and 18.4 kcal x mol(-1) due to the diastereomerization of the vinyl propellers. The resulting two signals observed at >360 K further coalesce at 425 K with a barrier of 22.9 kcal x mol(-1) due either to oxygen-to-oxygen proton exchange or to E/Z isomerization. The estimated upper limit for the rate of proton exchange of k(ex) < or = (2-4) x 10(3) M(-1) x s(-1) at 425 K between the enol molecules is sufficiently slow to be a rate-controlling step in the isomerization. A process in which several enol molecules catalyze the isomerization is suggested, and several mechanistic routes are analyzed.     

Carbon-13NMR spectra of isomeric diazaphenanthrenes,II δ-Effects in sterically crowded methyl derivatives

Steric downfield shifts due to a -CH moiety and a -nitrogen lone pair are similar in methylated diazaphenanthrenes. Most probably steric distortions are responsible for the -effects observed, and this might be quoted as a further evidence for a nearly equal steric requirement of a hydrogen atom and a nitrogen lone pair.

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C-13 NMR-Spektren isomerer Diazaphenanthrene, II. -Effekte in sterisch gehinderten Methylderivaten

Zusammenfassung Sterisch bedingte Tieffeldverschiebungen infolge von -CH-Molekülteilen und -lone pairs von Stickstoffatomen sind in methylierten Diazaphenanthrenen ähnlich. Die gemessenen -Effekte dürften auf sterische Deformationen zurückzuführen sein, was als weiteres Indiz für den nahezu gleichgroßen Raumbedarf eines Wasserstoffatoms und eines freien Elektronenpaars am Stickstoff gewertet werden kann.

     

A thermally stable and sterically unprotected terminal electrophilic phosphinidene complex of cobalt and its conversion to an eta(1)-phosphirene

The terminal chloroaminophosphido complex [Co(CO)3(PPh3){P(Cl)NiPr2}] is formed via reaction of K[Co(CO)4] with iPr2NPCl2 in the presence of triphenylphosphine. Chloride abstraction by aluminum trichloride leads to the first terminal phosphinidene complex of cobalt, [Co(CO)3(PPh3)(PNiPr2)][AlCl4]. The electrophilicity of the phosphinidene was demonstrated by its reaction with diphenylacetylene to form the phosphirene complex [Co(CO)3(PPh3){P(NiPr2)C(Ph)C(Ph)}][AlCl4].     

Direct synthesis of per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives

A convenient and direct per(poly)fluoroalkylmethyl-mtroducing cyclopropanation reaction was described. In the presence of CrCl3/Fe, per(poly)fluoroalkyl iodides reacted with diethyl allylmalonate and its analogs to give per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives in high yields. This reaction was considered to proceed by two steps: radical addition followed by cyclopropanation.     

Synthesis of sterically hindered phenolic compounds from indole and its derivatives

Reactions of 3,5-di-tert-butyl-4-hydroxybenzyl acetate with indole and its derivatives gave a series of sterically hindered phenolic compounds having various functional groups. The products are potentially capable of inhibiting radical chain oxidation processes according to different mechanisms.     

1,1-Bis(benzotriazolyl) derivatives as gem-dianion synthons

Bis(benzotriazolyl)methylbenzenes 1a,b were converted by excess lithium metal in the presence of ketones into the 1,3-diols 3a-g in moderate to good yields. However, similar treatment of 5 gave only the mono reduction products 6, 7. Compounds 1a,b reacted with 1 equivalent of diketone 8 to form olefins 10a,b.     

Stereoselectivity in the electrophilic addition reactions of stigmast-22(23)-ene derivatives

Oxidation of 5α-stigmast-22-en-3- one (1) with m-chloroperbenzoic acid afforded [22R,23R]-epoxide 3 and [22S, 23S]-epoxide 2, in a 5:3 ratio. Reaction of 1 with iodine/silver acetate gave a mixture of iodoacetates 8 and 9, which on treatment with base yielded the single epoxide 2. Those results suggest that electrophiles may preferentially approach the Δ²²-bond from the side of the 21-Me group, in accordance with observations with the ergosterol-like side chain.     

Atropisomeric (R,R)-2,2'-Bi([2]paracyclo[2](5,8)quinolinophane) and (R,R)-1,1'-Bi([2]paracyclo[2](5,8)isoquinolinophane): synthesis, structural analysis, and chiroptical properties

Atropisomeric (R,R)-2,2'-bi([2]paracyclo[2](5,8)quinolinophane) [(R,R)-1] and (R,R)-1,1'-bi([2]paracyclo[2](5,8)isoquinolinophane) [(R,R)-2] have been prepared in moderate overall yield (17 and 9%, respectively) by a four-step sequence starting from (R)-(-)-4-amino[2.2]paracyclophane and (R)-(-)-4-carboxy[2.2]paracyclophane, respectively. The structures have been determined on the basis of NOE (1)H NMR analysis and molecular mechanics (MM) calculations performed with a Spartan02 program, using the MMF94s force field. A preliminary, qualitative analysis of the chiroptical properties of these two compounds has also been attempted. The main spectral data can be interpreted in terms of an almost planar 2,2'-bisquinoline chromophore inserted in a paracyclophane structure in the case of (R,R)-1, while in the case of (R,R)-2, the main role is played by a distorted 1,1'-bisisoquinoline chromophore. On the basis of the above structural results, a hypothesis about the enantioselection capability of these two molecules has also been formulated.     

Formylporphyrins and their derivatives in the chemistry of porphyrins (review)

Data on the synthesis and chemical transformations of formylporphyrins obtained with the Vilsmeier reaction are generalized in the review. Special attention is focused on synthesis of dimeric porphyrins.     

Heterocyclization of 1,1-dicyano-2-(trifluoromethyl)ethylenes with 1,3,3-trimethyl-3,4-dihydroisoquinoline and its derivatives

1,3,3-Trimethyl-3,4-dihydroisoquinolines react with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene to give 4-amino-6,6-dimethyl-2,2-bis(trifluoromethyl)-3-cyano-6,7-dihydro-2H-benzo[a]quinolizines. The reaction of 3,3-dimethyl-1-cyanomethylidene-1,2,3,4-tetrahydroisoquinoline and the methyl ester of 3,3-dicyano-2-(trifluoromethyl)acrylic acid leads to 5,5-dimethyl-3-oxo-2-(trifluoromethyl)-2-(dicyanomethyl)-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinoline.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1888–1892, August, 1992.     

Stable gold(III) complexes with thiosemicarbazone derivatives

Novel thiosemicarbazonato complexes of gold(III) have been prepared from reactions of [Au(damp-C1,N)Cl2(damp- = 2-(N,N-dimethylaminomethyl)phenyl) or [NBu4][AuCl4] with 2-pyridineformamide thiosemicarbazones (HL). The thiosemicarbazones deprotonate and coordinate as mononegative, tridentate NNS ligands to gold to give [Au(Hdamp-C1)(L)]Cl2 or [AuCl(L)]Cl complexes. The organometallic damp- ligand is protonated during the reactions and the Au-N bond is cleaved. The [AuCl(L)]+ cations represent the first gold(III) complexes with thiourea derivatives which are not stabilised by an additional organometallic ligand. Reactions of [NBu4][AuX4](X = Cl, Br) with diphenylthiocarbazone (dithizone) result in reduction of the metal and the formation of gold(I) complexes of the composition [AuX(SCN4-3,4-Ph2)] where SCN4-3,4-Ph2 is 3,4-diphenyltetrazole thione which is formed from cyclisation of dithizone.     

Photogenerated electrophilic radicals for the umpolung of enolate chemistry

The use of enolate chemistry is the election choice when a CC bond formation is required exploiting the acidity of carbonyl derivatives in the α position. However, a reversed-polarity equivalent of enolate chemistry is emerging making use of electrophilic radicals having a radical site in place of a negative charge in the same α position. Visible light photoredox catalysis is becoming the ideal tool for the generation of these radicals thus allowing their wide application in several synthetic routes. Aim of this review is to collect recent examples of the chemistry of photogenerated electrophilic radicals for the forging of new CC or other CY bonds.     

Isostructural potassium and thallium salts of sterically crowded triazenes: a structural and computational study

Because of their similar cationic radii, potassium and thallium(I) compounds are usually regarded as closely related. Homologous molecular species containing either K(+) or Tl(+) are very rare, however. We have synthesized potassium and thallium salts MN3RR' derived from the biphenyl- or terphenyl-substituted triazenes Tph2N3H (1a), Dmp(Mph)N3H (1b), Dmp(Tph)N3H (1c), and (Me4Ter)2N3H (1d) (Dmp=2,6-Mes 2C6H3 with Mes=2,4,6-Me3C6H2; Me4Ter=2,6-(3,5-Me2C6H3)2C6H3; Mph=2-MesC6H4; Tph=2-TripC6H4 with Trip=2,4,6-(i)Pr3C6H2). The potassium complexes 2a- d were obtained in almost quantitative yield from the reaction of 1a- d with potassium metal in n-heptane. Metalation of 1a- d with TlOEt afforded the thallium triazenides 3a- d in high yields. All new compounds have been characterized by (1)H and (13)C NMR spectroscopy, elemental analysis, and X-ray crystallography and for selected species by melting point (not 3b), IR spectroscopy (2a, 2d, 3a, 3c, 3d), and mass spectrometry (2a, 3c). In the solid-state structures of monomeric 2a and 3a, quasi-monomeric 2b, 3b, 2c, and 3c, and dimeric 2d and 3d additional metal-eta (n)-pi-arene-interactions to the flanking arms of the biphenyl- and terphenyl groups in the triazenide ligands of decreasing hapticity n are observed. Remarkably, all homologous potassium and thallium complexes crystallize in isomorphous cells. For 2a and 3a, the nature of the M-N and M...C(arene) bonding was studied by density functional theory calculations.     

Redox-active antifungal cobalt(II) and copper(II) complexes with sterically hindered o-aminophenol derivatives

Co(II) complexes with 4,6-di(tert-butyl)-2-aminophenol (HL^I) and 2-anilino-4,6-di(tert-butyl)phenol (HL^II) have been synthesized and characterized by means of physico-chemical methods. The compounds HL^I and HL^II coordinate in their singly deprotonated forms and behave as bidentate O,N-coordinated ligands; their low-spin Co(II) complexes are characterized by CoN₂O₂ coordination modes and square planar geometry. Both the free ligands and their Co(II) and Cu(II) complexes (we have produced and characterized the latter before) exhibit a pronounced antifungal activity against Aspergillus niger, Fusarium spp., Mucor spp., Penicillium lividum, Botrytis cinerea, Alternaria alternata, Sclerotinia sclerotiorum, Monilia spp., which in a number of cases is comparable with that of Nystatin and Terbinafine or even higher. The reducing properties of the ligands and their metal(II) complexes, as well as their antifungal activities, were found to decrease in the order: Cu(L^I)₂ > Cu(L^II)₂ ? Co(L^I)₂ > Co(L^II)₂ > HL^I > HL^II.