Ferrocene Compounds. XXVII. Synthesis and Structure of 2-(Ferrocenylmethyl)propane-1,3-diol

The title compound was obtained by reduction of diethyl (ferrocenylmethyl)malonate with lithium aluminium hydride in diethyl ether. The structure of this novel ferrocene derivative was assigned by means of elemental analysis, IR, [¹H]NMR, and [¹³C]NMR spectroscopy. The structure was also confirmed by a single crystal X-ray study. The compound crystallizes in monoclinic P2₁/a space group with unit cell dimensions: a = 9.7360(6), b = 27.040(5), c = 14.767(3) Å, = 103.835(6)°, V = 3774.8(11) ų, Z = 12. The asymmetric unit contains three crystallographically independent molecules. In the ferrocenyl moieties, the Fe–C bond distance values are in the range 2.006(5)—2.051(3) Å and C–C distances in the range 1.366(7)–1.425(4) Å. The cyclopentadienyl rings in each of the molecules are mutually twisted by about 13° from the eclipsed conformation. The hydroxyl groups are involved in the intermolecular O–H...O hydrogen bond formation with O-O distances in the range 2.686(3)–2.801(4) Å forming infinite two-dimensional network in a [0 0 1] plane. The crystal structure is additionally stabilized by C–H-O weak intermolecular hydrogen bonds.     

Synthesis and study of organic nitrates of heterofunctional series. 5. Synthesis of 3,3-bis(hydroxymethyl)oxetane mono- and dinitrates and 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) mono- and dinitrates

New procedures were developed for the synthesis of 3,3-bis(hydroxymethyl)oxetane dinitrate (1) by O-nitration of the corresponding glycol (3) or its mononitrate (6), which were prepared by the reactions of 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) (2) mono- (4) and dinitrates (5), respectively, with alkali. A new method was devised for the synthesis of compounds 4 and 5 by the reaction of tetraol 2 with concentrated HNO₃ in dichloroethane. The structures of compounds 1 and 6 were established by X-ray diffraction analysis.     

α-(3,7-Dioxa-r-1-azabicyclo[3.3.0]oct-c-5-ylmethoxy)-diazines. Part 1: Synthesis and stereochemistry. Extension to s-triazine series

The general and efficient synthesis of the title compounds, consisting of the (selective) replacement of chlorine in commercial α-chlorodiazines and cyanuryl chloride by the 3,7-dioxa-r-1-azabicyclo[3.3.0]oct-c-5-ylmethoxy group (Williamson method) is described. The stereochemistry of this new series of derivatives is analysed in terms of different conformational chirality exhibited in solution (¹H NMR) versus solid state (X-ray diffractometry), meso against chiral forms, respectively. In solid state, the inclusion capacity of some chiral networks as well as their supramolecular aggregation is pointed out. A good correlation between rotameric behaviour of the c-5-di(s-tri)diazinyloxymethyl group in the two states is found.     

α-(3,7-Dioxa-r-1-azabicyclo[3.3.0]oct-c-5-ylmethoxy)-diazines. Part 2: Functionalisation via directed ortho-metallation and cross-coupling reactions

The functionalisation of the title compounds via regioselective Directed ortho-Metallation (DoM) and cross-coupling reactions is studied. The compatibility of the 3,7-DiOxa-r-1-AzaBicyclo[3.3.0]Oct-c-5-ylmethoxy system (DOABO-CH₂O) to typical reaction conditions is established. Its role as Directed ortho-Metallation Group (DoMG) is examined, including competition with classical DoMGs, chlorine and methoxy. The chelating ability of some functionalised terms such as DOABO-CH₂O substituting chiral diarylmethanols and polyaza analogues of 2,6-terpyridine is discussed as intramolecular steric relationships determining configuration and aptitude to bind selectively transition metals, respectively.     

Synthesis and Crystal Structure of （2S,5S）-1-Aza-2-（2-pyridyl）-3-oxa-4,4-diphenylbicyclo [3.3.0] Octane

1 INTRODUCTION The catalytic asymmetric synthesis has been a challenging subject in organic synthesis. The deve- lopment of efficient enantioselective catalysts appli- cable to a wide range of carbon-carbon bond form- ing reactions represents a pivotal …     

Synthesis of (±)-9-[c-4, t-5-bis(hydroxymethyl)cyclopent-2-en-r-1-yl]-9H-adenine (BCA) derivatives branched at the 4′-position based on intramolecular SH2′ cyclization

Synthesis of 4′-branched BCA analogues (5) was carried out. Stereospecific construction of the cis-disposed 4′-carbon-substituents and 5′-hydroxymethyl group was secured by employing the bicyclo[3.3.0]lactone 16 as a key intermediate, which was prepared by radical-mediated intramolecular S_H2′ cyclization of the phenylselenomethyl ester 15. After manipulation of the double bond of 16, bis(Boc)adenine was introduced based on the Mitsunobu reaction of the allyl alcohol 24. Transformation of the lactone function of 27 allowed preparation of the 4′-hydroxymethyl (31), the 4′-vinyl (32), the 4′-cyano (34), and the 4′-ethynyl (35) derivatives. Anti-HIV and anti-HCV activities of the free nucleosides 36-38 were also examined.     

2-Amino-5,5-bis(hydroxymethyl)-1,3-thiazol-4(5H)-one and its spirodioxane compounds in the Mannich reaction

It was found that the aminomethylation of 2-amino-5,5-bis(hydroxymethyl)-1,3-thiazol-4(5H)-one and its spiro analogs using primary amines is accompanied by cyclization at the amidine fragment of the molecule with annelation of a tetrahydrotriazine ring. When using secondary amines the aminomethylation occurs at the exocyclic nitrogen atom. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1252–1260, August, 2006.     

Synthetic approaches to physiologically active polycyclic compounds: VII. Synthesis of 2-(7-Hydroxybicyclo-[3.3.1]non-3-ylmethyl)propane-1,3-diol

2-(endo-7-Hydroxybicyclo[3.3.1]non-exo-3-ylmethyl)propane-1,3-diol was synthesized in seven steps starting from endo-7-hydroxybicyclo[3.3.1]nonane-exo-3-carboxylic acid. The title compound attracts interest as intermediate product for the synthesis of potential tubulin ligands.     

Synthesis of trifluoromethyl-substituted salicylates by cyclocondensation of 1,3-bis(silyloxy)-1,3-butadienes with 4,4-dimethylthio-1,1,1-trifluorobut-3-en-2-one

A formal [3+3] cyclocondensation of 1,3-bis(silyl enol ethers) with the little-known 4,4-dimethylthio-1,1,1-trifluorobut-3-en-2-one was studied. In contrast to 4,4-dimethoxy-1,1,1-trifluorobut-3-en-2-one, this α-oxoketene dithioacetal reacts with 1,3-bis(trimethylsilyloxy)-1,3-butadienes in the presence of TiCl₄ to give mainly 6-methylthio-4-(trifluoromethyl)salicylates via 1,2-addition. The scope and limitations of the reaction are discussed.     

Mass spectral fragmentation of (S,S)-2-substituted 4,4-diphenyl-3,1-oxazabicyclo[3.3.0]octanes: ring contraction of pyrrolidine and 1,3-oxazolidine in mass spectrometry

The mass spectral behaviour of (S,S)-2-substituted 4,4-diphenyl-3,1-oxazabicyclo[3.3.0]octanes has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under fast atom bombardment (FAB) and electron impact (EI) ionization conditions. Under FAB ionization, all compounds show a tendency to form protonated aldehyde or benzophenone ions and to form protonated 1-azabicyclo[3.1.0]hexane ions, which can further lose an ethylene or cyclopropane from the pyrrolidine ring to produce protonated 1-azabicyclo[1.1.0]butane ions and 3H-azirine ions, respectively. Under EI ionization, a similar fragmentation to that under FAB ionization was observed. The title compounds also show a tendency to yield oxirane ions and oxirenium ions by loss of pyrrolidine and pyrrolidine plus H. Ring contractions of 1,3-oxazolidine by loss of an aldehyde or ketone and of pyrrolidine by loss of an ethylene or cyclopropane were observed under both FAB and EI ionization conditions.     

Highly efficient synthesis of chromeno[2,3-b]pyridine using Graphene-Oxide/N1,N3-bis (pyridin-2-ylmethyl)propane-1,3-diamine-Copper nanocomposites as a novel catalyst

Recent studies about innovations in GO/N-Ligand-Cu Nano-Composites have been done. Graphene-Oxide is improved with N¹,N³-bis (pyridin-2-ylmethyl)propane-1,3-diamine and after that is matched with copper (Cu). The chemical composition and the structure of the catalyst were analyzed by TGA/DTG, EDX, XRD, FT-IR, TEM, and SEM. The results demonstrated that GO/N-Ligand-Cu was able to catalyze the chromeno[2,3-b]pyridine compounds to obtain high yields in short reaction time. The results of the present work are hoped to assist the growth of a new class of heterogeneous catalysts as the high-function candidate for industrial applications.     

One-pot electrosynthesis of 2,3-bis(spiro-2-indanyl-1,3-dione)-indeno[1,2-b]furan-4-one

The 2,3-bis(spiro-2-indanyl-1,3-dione)-indeno[1,2-b]furan-4-one has been synthesized by cathodic reduction of 2,2-dibromo-1,3-indandione in dichloromethane-Bu₄NBF₄. In contrast, tris-indanedione was the main product when acetonitrile was used as a solvent. Sunlight exposition of the dispiro compound afforded the tris-indandione in quantitative yield.     

New tetradentate Schiff-base polymers: preparation of poly[2,5-(didodecyloxy)phenylene-1,4-diyl-alt-N,N-(o-phenylene)-bis(salicylideneiminato-4,4-diyl)] and poly[2,5-(didodecyloxy)phenylene-1,4-diyl-alt-N,N-(alkylidene)-bis(salicylideneiminato-4,4-diyl)]s

New tetradentate Schiff-base polymers, in which phenylene units alternate with salicylideneiminato units, have been prepared by condensation of 2,5-(didodecyloxy)-1,4-bis(3-formyl-4-hydroxyphenyl)benzene (DFHB) with appropriate diamines in a mixed solution of CHCl₃/toluene/acetic acid with 31-79% yields. DFHB as the key building block was prepared by the Suzuki reaction of 2,5-(didodecyloxy)benzene-1,4-diboronic acid with 5-bromosalicylaldehyde in a two-phase solution of tetrahydrofuran/water in the presence of NaHCO₃/Pd(PPh₃)₄ in 45% yield. The molecular structures of the prepared compounds were identified by spectroscopy. Their absorption spectroscopic profiles have been analyzed.     

Diastereoselective reaction of (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol with aromatic aldehydes. Synthesis of (1R,2R,4S,5S,8S)-2,8-diaryl-4-(4-nitrophenyl)-1-aza-3,7-dioxabicyclo[3.3.0]octanes

We have synthesized a series of (1R,2R,4S,5S,8S)-2,8-diaryl-4-(4-nitrophenyl)-1-aza-3,7-dioxabicyclo[3.3.0]octanes as a result of reaction of (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol with aromatic aldehydes. The structure of the compounds obtained was established on the basis of ¹H NMR data. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 757–763, May, 2006.     

Synthesis of 7-hydroxy-2-(2-hydroxybenzoyl)benzo[c]chromen-6-ones by sequential application of domino reactions of 1,3-bis(silyl enol ethers) with benzopyrylium triflates

The domino, Michael-retro-Michael-aldol, reaction of 2,4-bis(trimethylsilyloxy)penta-1,3-diene with 3-formylchromones afforded 4-(2-hydroxybenzoyl)-2-acetylphenols, which were transformed into 6-(2-hydroxybenzoyl)chromones. The Me₃SiOTf-mediated condensation of the latter with 1,3-bis(silyl enol ethers) and subsequent domino ‘retro-Michael-aldol-lactonization’ reaction afforded 7-hydroxy-2-(2-hydroxybenzoyl)benzo[c]chromen-6-ones.     

Methanol facilitated synthesis of 7-methoxy-2-thioxo-2,3-dihydro-1H-1,3-diazepin-4(7H)-ones from nitroallylic acetates and thiourea

A novel efficient strategy for the synthesis of rare 7-methoxy-2-thioxo-2,3-dihydro-1H-1,3-diazepin-4(7H)-ones is described. Methanol, solvent for this one-step reaction, participated in this seven-membered ring closure reaction between nitroallylic acetates and thiourea. The thiourea itself also served as a base in this reaction. A possible mechanism for the reaction is proposed.     

Regioselective synthesis of benzo[c]chromen-6-ones by one-pot cyclocondensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 4-chloro-2-oxo-2H-chromene-3-carbaldehyde

The cyclocondensation of 4-chloro-2-oxo-2H-chromene-3-carbaldehyde with 1,3-bis(silyloxy)-1,3-butadienes provides a convenient synthesis of benzo[c]chromen-6-ones.