Total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide γ-butyrolactones

The first total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide was achieved in a convergent pathway. The salient features of our synthesis include Ohira–Bestmann reaction, regioselective alkyne addition to terminal epoxide, TEMPO/BAIB mediated oxidative lactonization, and partial hydrogenation.     

Total synthesis of two γ-butyrolactone containing compounds (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide

The first total synthesis of (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide was accomplished using Jacobsen hydrolytic kinetic resolution, Ohira–Bestmann reaction, regioselective alkyne addition to terminal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated oxidative lactonization and partial hydrogenation as the key steps.     

Synthesis of novel spiro[benzo[4,5]thiazolo[3,2-a]chromeno[2,3-d]pyrimidine-14,3′-indoline]-1,2′,13(2H)-triones via three component reaction

A new and efficient method for the synthesis of hitherto unreported spiro[benzo[4,5]thiazolo[3,2-a]chromeno[2,3-d]pyrimidine-14,3′-indoline]-1,2′,13(2H)-triones was developed via the Domino Knoevenagel condensation–Michael addition–intermolecular cyclization sequences of isatin derivatives, cyclohexane-1,3-diones, and 2-hydroxy-4H-benzo[4,5]thiazolo[3,2-a]pyrimidin-4-ones, employing 12-tungstophosphoric acid (H₃PW₁₂O₄₀) as an effective and inexpensive catalyst.     

One-pot heterocyclic ring closure of 1,1′-bi-2-naphthol to 7H-dibenzo[c,g]carbazole

An operationally simple ring closure of racemic 1,1′-bi-2-naphthol (BINOL) yielded the heterocyclic aromatic compound 7H-dibenzo[c,g]carbazole (DBC). This one-pot method gave a good conversion and is suitable for gram-scale synthesis. DBC derivatives have high thermal durability, amorphous and crystalline structures with unique morphological properties, and semi-conducting behavior with potential applications in organic electronics.     

2-[Pyridin-2(4)-yl]-N-[ω-vinyloxyalkyl]ethanamines

Russian Journal of Organic Chemistry -     

N- vs O-Coordination in cyclomanganation of 1,5-diaryl-3-(2-pyridyl)pentane-1,5-diones and 3-(2-pyridyl)chalcones; cyclomanganation at saturated carbon and the crystal structure of [1,5-diphenyl-κC-3-(2-pyridyl- κN)pentan-2-yl-κC-1,5-dione-κOκO]tetracarbonylmanganesetricarbonylmanganese

Reaction of 1,5-diphenyl-3-(2-pyridyl)pentane-1,5-dione (5a) with 2.5 moles of benzylpentacarbonylmanganese in petroleum spirit under reflux gives a small amount of the symmetric di-aryl-manganated product [1,5-diphenyl-κC²-3-(2-pyridyl)pentane-1,5-dione-κO¹κO⁵]bis-(tetracarbonylmanganese) (7a), but mostly [1,5-diphenyl-κC²-3-(2-pyridyl-κN)pentan-2-yl- κC²-1,5-dione-κO¹κO⁵]tetracarbonylmanganesetricarbonylmanganese (6a) which is manganated at only one aryl carbon [by Mn(CO)₄] but also [by Mn(CO)₃ with N and O coordination] at the methylene carbon adjacent to the Mn(CO)₄-coordinated ketone carbonyl. The latter is a rare example of direct cyclomanganation at a saturated carbon and the only known case adjacent to a carbonyl group; the X-ray crystal structure of 6a is reported. With 3 moles of benzylpentacarbonylmanganese the yield of 6a remains unchanged but some trimanganation product [1,5-diphenyl-κC^2′κC^2?-3-(2-pyridyl-κN)pentan-2-yl-κC²-1,5-dione-κO¹κO⁵]tris-(tetracarbonylmanganese) (8a) is formed, presumably from 7a. Routes to products are proposed and activating factors considered. 1,5-Di-(2-thienyl)-3-(2-pyridyl)pentane-1,5-dione (5b) and its 3-thienyl isomer (5c) similarly give 6a analogues [1,5-di-(2-thienyl-κC³)-3-(2-pyridyl-κN)pentan-2-yl-κC²-1,5-dione-κO¹κO⁵]tetracarbonylmanganesetricarbonylmanganese (6b) and [1,5-di-(3-thienyl-κC²)-3-(2-pyridyl-κN)pentan-2-yl-κC²-1,5-dione-κO¹κO⁵]tetracarbonylmanganesetricarbonylmanganese (6c).Also reported are the mono-cyclomanganation product [1-(2,6-dimethoxyphenyl)-3-(2-pyridyl-κN)prop-2-en-2-yl-κC²-1-one]tetracarbonylmanganese (16) and dicyclomanganation product [1-(2,5-dimethyl-3-thienyl-κC⁴)-3-(2-pyridyl-κN)prop-2-en-2-yl- κC²-1-one-κO ]bis-(tetracarbonylmanganese) (17) from reaction of the respective (E)-1-aryl-3-(2-pyridyl)prop-2-en-1-ones (3-(2-pyridyl)chalcones), the first reported examples of enone metallation at the α-carbon via N-coordination by a β-2-pyridyl group.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

Aminolithiation–arylation consecutive cyclization of N-(2-fluorophenyl)methylaminoalkylstyryls giving aryl-substituted pyrido[1,2-b]isoquinolines

Aminolithiation–arylation tandem cyclization of N-(2-fluorophenyl)methylaminoalkylstyryls proceeded smoothly to give hexahydro-2H-pyrido[1,2-b]isoquinoline using a stoichiometric amount of n-BuLi with high trans selectivity. The arylation reaction was highly accelerated by the addition of HMPA. Both pyrido- and pyrrolo-[1,2-b]isoquinoline were successfully constructed by this tandem reaction.     

Four-component synthesis of alkyl [2-[(cyclohexylamino)carbonyl]-4-oxo-2H-chromen-3(4H)-ylidene]methyl 3,4,5,6-tetrahalophthalates via a domino O-acylation/α-addition cyclization/alcoholysis sequence

A novel protocol was developed for the synthesis of alkyl [2-[(cyclohexylamino)carbonyl]-4-oxo-2H-chromen-3(4H)-ylidene]methyl 3,4,5,6-tetrahalophthalate derivatives via the one-pot, four-component domino O-acylation/α-addition cyclization/alcoholysis reaction of tetrahalophthalic anhydrides, 3-formylchromones, cyclohexyl isocyanide and various alcohols. The highlights of this novel cascade reaction include mild reaction conditions, easy workup, and high bond efficiency resulting in the formation of four new bonds (two CO, one CO and one CC) in a single operation.     

Some reactions of [(η6-C6Me6)Ru(η6-[2.2]paracyclophane)]-[BF4]2 with nucleophiles

Single addition of the nucleophiles X⁻ (X = H, CN, OH) to the less sterically hindered ring in [(η⁶-C₆Me₆)Ru(η⁶-C₁₆H₁₆)][BF₄]₂ (1) proceeds smoothly to produce, as the sole product, [(exo-η⁵-C₆Me₆X)Ru(η⁶-C₁₆H₁₆)][BF₄]. Use of Na[BD₄] in place of Na[BH₄] gives the expected shift in ν(C-H_exo) in the infrared spectrum.     

Substituted benzoquinazolinones. Part 1: Synthesis of 6-aminobenzo[h]quinazolinones via Buchwald–Hartwig amination from 6-bromobenzo[h]quinazolinones

6-(Morpholin-4-yl)benzo[h]quinazolin-4(3H)-one derivatives 18a,b were prepared under Buchwald–Hartwig conditions by reacting 6-bromobenzo[h]quinazolin-4(3H)-ones 13a,b with morpholine in the presence of a Pd(OAc)₂/XantPhos system in 1,4-dioxane as solvent. The starting 6-bromobenzo[h]quinazolin-4(3H)-ones 13 were synthesized via condensation of the ethyl 1-amino-4-bromonaphthalene-2-carboxylate (11) with formamide (Niementowski reaction), and then reaction of the obtained benzoquinazolinone 9 with appropriates benzyl bromides. Compound 11 was prepared using a three-step procedure involving (a) metalation of the N-Boc- or N-Piv-protected 1-aminonaphthalenes with t-BuLi, followed by reaction with ethyl chloroformate, (b) bromination of the naphthalene ring of ester 3 using NBS, and next (c) deprotecion of the amine group with TFA or HCl. Biological screening of the potential cytotoxicity of compounds 8, 9, 18b on A549 and HT29 cell lines, as well as on the lymphocytes showed that compound 18b has interesting anticancer activities. The detailed synthesis, spectroscopic data, and biological assays were reported.     

Host compounds (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (TETROL) and (2R,3R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT) with guests o-, m- and p- toluidine: A comparative investigation

In this work, we have compared the host abilities of closely related compounds (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (TETROL) and (2R,3R)-(?)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT) when these were recrystallized from single and mixed toluidine guests. Significant differences in host behaviour and selectivities were revealed and these were explained by means of single crystal diffraction experiments. Thermal analyses were used to determine the relative complex stabilities, and these data correlated exactly with the host selectivity orders for both TETROL and DMT.     

Synthesis of 2-aryl-2H-[1,2,4]triazoloquinolin-3-one and 2-aryl-2H-[1,2,4]triazoloisoquinolin-3-one derivatives from α-chloroformylarylhydrazines hydrochloride

The reaction of α-chloroformylarylhydrazines hydrochloride with quinoline under air provided the corresponding 2-aryl-2H-[1,2,4]triazoloquinolin-3-ones 3a-3d in 33-42% yields and unexpected isomeric 2-aryl-2H-[1,2,4]triazoloisoquinolin-3-ones 4a-4d in 30-42% yields. These two isomers were isolated and fully characterized by spectroscopic methods including X-ray crystallography. By employing 3-methylquinoline as the starting material under the same condition, the reaction only gave compound 3e-3h as sole products in 70-82% yields without the formation of isomers. A plausible mechanism was proposed through electrophilic aromatic reaction, the tandem ring cyclization and ring-opening, and oxidation for the generation of 2-aryl-2H-[1,2,4]triazoloisoquinolin-3-ones (4).     

4-(4-Chlorophenyl)-3,7,7-trimethyl-1-[2-(4-nitrobenzoyl)ethyl]-4,7,8,9-tetrahydro-1H-pyrazolo[3,4-b]quinolin-5(6H)-one–ethanol (1/1)

Molecules of the title compound, C₂₈H₂₇ClN₄O₄·C₂H₆O, form a C(6) chain via an N—H⋯O hydrogen bond along the c axis by the operation of a c-glide plane, with N⋯O = 2.761 (3) Å and N—H⋯O = 165°. The mol­ecules are further linked by a weak C—H⋯O interaction, with C⋯O = 3.344 (4) Å and C—H⋯O = 150°. Pendant hydrogen-bonded ethanol solvent mol­ecules are attached to the chains by O—H⋯N hydrogen bonds, with O⋯N = 2.904 (3) Å and O—H⋯N = 175°.     

超分子化合物[2-(吡啶-4-基)苯并咪唑]·[SnCl_6]的水热合成及晶体结构

采用水热法合成了一个新的超分子化合物[PyBImH_2]·[Sn Cl6](Py BIm=2-(4-吡啶基)苯并咪唑),并用元素分析、红外光谱、荧光光谱及X射线单晶衍射对其进行了表征。化合物属于正交晶系,Pbcn空间群,晶胞参数:a=7.1468(3),b=15.0493(6),c=16.1195(8),V=1733.72(13)3,Z=4,Dc=2.025g/cm3,Mr=528.63,μ(Mo Kα)=2.395mm~(-1),F(000)=1024,R_1=0.0264,wR_2=0.0665。Sn~(4+)与6个氯离子配位,形成八面体的配位几何。配位阴离子[SnCl_6]~(2-)与阳离子[PyBImH_2]~(2+)通过氢键及π-π堆积作用形成三维超分子结构。     

Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN,and [Ph4Sb]+2[ZrCl6]2–

Russian Chemical Bulletin - The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–?MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–?2 MeCN (3), and...     

3H-Pyrroles as a platform for the catalyst-free construction of dihydropyrrolo[2,1-b]oxazoles: [4 + 2]-cycloaddition vs [2 + 3]-annulation with 1-cyano-3-hydroxyalkynes

Non-aromatic pyrrole isomers, 3,3-dialkyl-2-aryl-3H-pyrroles, were reacted with 1-cyano-3-hydroxyalkynes under mild, catalyst-free conditions (20–60?°C) to regio- and stereoselectively afford (Z)-2-(dihydropyrrolo[2,1-b]oxazolylidene)acetonitriles in 62–82% yield, thus evidencing the preference for [2?+?3]-annulation over the [4?+?2]-Diels-Alder alternative. The reaction involves initial nucleophilic addition of the pyrrole moiety at the triple bond followed by tandem ring closure of an anionic intermediate.     

STRUCTURE OF CHLORO [2-2''''-PYRIDYL)-6-MSTHYLBEHZOTHIAZOLE] PYROCATECHOLATOANTIMONY(Ⅲ)

<正> C19H14N2O2ClSSb,Mr = 491.6, space group P1, a = 5.977(1), b= 8.708(1), c = 8.962(1) X, a=93.91(1),B= 103.25(1),r=94.80(1), V = 450.6 A3, Z = 1, Do = 1.79, DC = 1.812 g.cm-3,F(000) = 242,u(MoKa)= 18.1 cm-1,R=0.024 for 2903 reflections. The Sb atom is situated in a distorted square- pyramidal ( octahedral) environment, with Sb-Cl 2.546(2), Sb-0 2.004(2)/2.038(3), and Sb-N 2.442(3)/2.526(3)A.     

Synthesis of 1H-benzo[g]indazole derivatives: propargyl–allenyl isomerization and 6π-electrocyclization involving two aromatic π-bonds

An efficient synthesis of 1H-benzo[g]indazoles starting from Morita–Baylis–Hillman (MBH) adducts is disclosed. The synthesis was carried out from MBH bromide via a sequential copper-catalyzed alkynylation, one-pot synthesis of pyrazole, propargyl–allenyl isomerization, and a 6π-electrocyclization involving two aromatic π-bonds and an allenyl π-bond.     

[Pt2(P2O5H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d8配合物[Pt2(P2O5H2)4]4-和[Pt2(P2O4CH4)4]4-的基态和激发态结构.结果表明基态Pt-Pt距离分别为0.2905和0.2987nm,与实验的0.2925和0.2980nm符合.NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质.CIS计算揭示电子激发到Pt-Pt的σ(pz)成键轨道使得相互作用增强.保持激发态几何,含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475nm,与实验值512和510nm接近.