Two new flavonoid diglycosides from Cephalotaxus sinensis

Two new acetylated flavonoid diglycosides, scutellarein-5-O-[a-L-rhamnopyranosyl-(1→ 4)-b-D-6-O-acetylglucopyranoside] (1), apigenin-5-O-[a-L-rhamnopyranosyl-(1→2)-b-D-3,6-di-O-acetylglucopyranoside] (2), were isolated from the leaves of Cephalotaxus sinensis. Their structures were determined by chemical and spectroscopic methods including HR-FAB-MS, 1H–1H COSY, HSQC and HMBC experiments.     

Two new C-glycosylflavones from Mimosa pudica

Two new C-glycosylflavones were isolated from the whole plant of Mimosa pudica,and their structures were determined as 6,7,3′,4′-tetrahydroxyl-8-C-[α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranosyl flavone(1),5,7,3′,4′-tetrahydroxy-8-C[β-D- apiose-(1→4)]-β-D-glycopyranosyl flavone (2).Their structures elucidated by chemical and spectroscopic analysis including IR,MS,1D and 2D NMR spectra.     

Furostanol saponins with inhibitory action against COX-2 production from Tupistra chinensis rhizomes

Two furostanol saponins were obtained from the n-butanol fraction of methanol extract from Tupistra chinensis rhizomes,a folk medicine of Shennongjia Forest District of Hubei Province.Their structures were determined as (25S)-26-O-(β-D-glucopyranosyl)- furost-1β,3β,22α,26-tetrol-3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside (1) and (25R)- 26-O-(β-D-glucopyranosyl)-furost-1β,3β22α,26-tetrol 3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glu- copyranoside (2),on basis of chemical and spectroscopic evidences.1 and 2 displayed marked inhibitory action towards COX-2 production in macrophages of the rat abdomen induced by LPS at 20μg/mL.     

Synthesis of an antimetastatic tetrasaccharide β-D-Gal-(1→4)-β-d-GlcpNAc-(1→6)-α-D-Manp-(1→6)-β-D-Manp-OMe

An antimetastatic tetrasaccharide T₁,β-D-Gal-（1→4）-β-D-GlcpNAc-（1→6）-α-D-Manp-（1→6）-β-D-Manp-OMe,was synthesized with two approaches.The first approach was a conventional method employing thioglycoside and Koenigs-Knorr glycosylation reaction in 24%overall yield.The second one was a novel route through the azidoiodo-glycosylation strategy by using 2-iodo-2-deoxylactosyl azide as the donor in 36%overall yield.     

Two new saponins from Anemarrhena asphodeloides Bge.

Two new saponins 3-O-β-D-glucopyranosyl (1→2)-β-D-mannopyranosyl sarsasapogenin, named timosaponin A IV(1) and (5β, 25S)-26-O-β-D-glucopyranosyl-furost-20(22)-en-3,26-diol-3-O-β-D-glucopyranosyl (1→4) glucopyranosyl (1→2)-β-D-galacopyranoside, named timosaponin B IV(2), were isolated by silica gel column chromatography and preparative HPLC from Anemarrhena asphodeloides Bge. Their structures were elucidated by chemical characters and spectroscopic analysis.     

Synthesis ofa trimeric lignin model compound composed ofol-O-4 and β-O-4 linkages under microwave irradiation

A trimeric lignin model compound composed of α-O-4 and β-O-4 linkages was prepared by the microwave-assisted synthesis, which consisted of three steps： （a） the synthesis of 3-methoxy-4- benzyloxyacetophenone （2） from acetovanillone （1）, （b） the bromination of compound 2 to produce 3- methoxy-4-benzyloxy-α-bromoacetophenone （3）, and （c） followed by a nucleophilic substitution of compound （3） to obtain 3-methoxy-4-benzyloxy-α-（3-methoxy-4-（1-propenyl）phenol）-acetophenone （4）. The target product was characterized by MS, 1H NMR and 13C NMR spectroscopy. It was found that the trimeric compound synthesized can be used as a preferable lignin model compound because it contains guaiacyl structural unit （3-methoxy-4-hydroxy phenyl propane） linked by α-O-4 and β-O-4 linkages. In addition, under the conditions of microwave irradiation, the reaction time of each step is significantly reduced, and the selectivity of target product is greatly improved. The yields of each step and the overall sequence are 95.31%. 87.3%. 90.6% and 75.4% （95.31%× 87.3% × 90.6%）. respectively.     

Synthesis and structure elucidation of 25,26,27,28-tetramethylcalix[4]arene tetraketone using 1D and 2D NMR spectroscopies

The ¹H and ¹³C NMR spectra of the new calix[4]arene-based tetraketone were completely assigned by one- and two-dimensional homo- and heteronuclear experiments (¹H–¹H COSY, ¹H–¹³C HMQC, and HMBC) at 400 and 100 MHz, respectively, at 25 °C standard pulse sequence. ¹H and ¹³C spectra were measured at room temperature for 25,26,27,28-tetramethylcalix[4]arene tetraketone (1). ¹³C{¹H}, DEPT and NMR techniques were used to distinguish the methyl, methylene and methine carbon resonance signals of calix[4]arene 1. Correlation of 1D (¹H, ¹³C{¹H}, DEPT) and 2D (HMQC and HMBC) NMR data was used to completely assign various overlapping and broad signals of calix[4]arene 1. Heteronuclear multibond correlation (HMBC) studies were used to completely assign various carbon resonances. Our results show that the conformation of calix[4]arene 1 in the solution is very similar to the cone conformation reported in the literature.     

Synthesis and characterization of novel intramolecularly O,C,O-coordinated heteroleptic organostannylenes and their tungstenpentacarbonyl complexes

The syntheses are reported of the novel heteroleptic organostannylenes [2,6-(ROCH₂)₂C₆H₃]SnCl (1, R = Me; 2, R = t-Bu) and of their tungstenpentacarbonyl complexes [2,6-(ROCH₂)₂C₆H₃](X)SnW(CO)₅ (3, X = Cl, R = Me; 4, X = Cl, R = t-Bu; 5, X = H, R = Me). The compounds were characterized by means of elemental analyses, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopies, electrospray mass spectrometry and in case of 3 and 4 also by single crystal X-ray diffraction analysis. For the two latter compounds the substituents bound at the ether oxygen atom control the strength of intramolecular O → Sn coordination. Thus, the O–Sn distances amount to 2.391(5)/2.389(5) (3) and 2.464(3)/2.513(3) Å (4).     

Synthesis,method optimization,anticancer activity of 2,3,7-trisubstituted Quinazoline derivatives and targeting EGFR-tyrosine kinase by rational approach: 1st Cancer Update

A novel 3-(substituted benzylideneamino)-7-chloro-2-phenyl quinazoline-4(3H)-one (7–27) has been synthesized and characterised by IR, ¹H NMR, ¹³C NMR spectroscopy, and elemental analysis. We changed the methodology for the synthesis of 3-amino 7-chloro-2-phenyl quinazolin-4(3H)-one 6 to fusion reaction at 250 °C, instead of using solvent, to avoid the problem of ring opening, which is commonly observed while synthesizing quinazolines from benzoxazinone. NCI selected, 7-chloro-3-{[(4-chlorophenyl) methylidene] amino}-2-phenylquinazolin-4(3H)-one 12, with GI₅₀ value of ?5.59 M, TGI value of ?5.12 M, and LC₅₀ value of ?4.40 M showed remarkable activity against CNS SNB-75 Cancer cell line. Rational approach and QSAR techniques enabled the understanding of the pharmacophoric requirement for 2,3,7-tri substituted quinazoline derivatives to inhibit EGFR-tyrosine kinase as antitumor agents and could be used as an excellent framework in this field that may lead to discovery of potent anti tumor agent.     

Catalytic dehydrocoupling of thienyl/furyl-substituted carbosilanes – Synthesis and characterization of functional poly(hydrosilane)s [RMe2Si(CH2)xSiH]n, (R = 2-Th, 4-Me-2-Th, 2-Fu, 5-Me-2-Fu; x = 2 and 3)

The carbosilanes RMe₂Si(CH₂)_xSiH₃, [R = 2-Th (1a, 2a), 4-Me-2-Th (3a, 4a), 2-Fu (5a, 6a), 5-Me-2-Fu (7a, 8a); x = 2 and 3], with primary SiH₃ end groups undergo a facile dehydropolymerization under ambient conditions (50 °C, 48 h) in presence of Cp₂TiCl₂/2.2 n-BuLi catalyst to afford the corresponding poly(hydrosilane)s 1–8 bearing carbosilyl side chains appended with thienyl/furyl groups. These have been characterized by GPC, IR, multinuclear (¹H, ¹³C{¹H}, ²⁹Si{¹H}) NMR, UV and PL spectral studies.     

Synthesis and molecular modeling study of Cu(Ⅱ) complexes derived from 2-(diphenylmethylene)hydrazinecarbothioamide derivatives with cholinesterase inhibitory activities

Thiosemicarbazones of 2-amino-5-chlorobenzophenone and 3-aminobenzophenone（L¹-L⁴） have been synthesized and their Cu（Ⅱ） complexes（1-4） were afforded via coordination with cupric chloride.All these compounds were characterized by UV-vis and IR spectroscopy together with CHN elemental analysis.NMR spectroscopy was also applied to characterize the ligands.In vitro chohnesterase inhibitory assays for the complexes（1-4） showed IC₅₀ values less than 10μmol/L,with complex 1 exhibiting the most activity,IC₅₀=2.15μmol/L and 2.16μmol/L for AChE and BuChE,respectively. Molecular modeling simulation revealed the binding interaction template for complex 1 with the AChE and BuChE receptors.In DPPH assay,the complexes also showed more in vitro antioxidant activities in comparison to their parent ligands.     

Conformational and stereoelectronic investigation of chloromethyl methyl sulfide and its sulfinyl and sulfonyl analogs

Three compounds based on polyoxometalate building blocks, [Cu(en)₂]{[Cu(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(PO₄)]} · 4H₂O (1), [Co(en)₂]{[Co(en)₂]₂[HMo^VI₄Mo^V₄V^IV₈O₄₀(PO₄)]} · 5H₂O (2) and [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(VO₄)]} · 2H₂O (3) (en = ethylenediamine), have been synthesized and characterized by elemental analysis, IR, XPS, XRD, TGA and single-crystal X-ray diffraction analysis. The result of structure determination shows that isomorphic compounds 1, 2 and 3 feature a one-dimensional chain built from the reduced tetra-capped pseudo-Keggin polyoxoanion, which is further interconnected by [M(en)₂]²⁺ (M = Cu, Co and Ni) groups via the terminal oxygen atoms of polyoxoanions. The crystal data for these compounds are the following: 1, monoclinic, space group C2/c, a = 26.702(3) Å, b = 13.4539(14) Å, c = 19.5987(19) Å, β = 108.650(2)°, V = 6671.0(12) Å³, Z = 4; 2, monoclinic, space group C2/c, a = 26.244(3) Å, b = 13.5070(17) Å, c = 19.581(3) Å, β = 106.881(2)°, V = 6641.8(15) Å³, Z = 4; 3, monoclinic, space group C2/c, a = 26.2789(15) Å, b = 13.5408(6) Å, c = 19.6312(9) Å, β = 106.2590(10)°, V = 6706.1(6) Å³, Z = 4. Variable-temperature magnetic susceptibility measurements of compounds 1 and 3 reveal the feature of antiferromagnetic exchange in these compounds.     

Novel metallophthalocyanines bearing 3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,4-triazole bulky substituents by microwave irradiation

The synthesis of metallophthalocyanines [6–9; M = Ni(II), Zn(II), Co(II) and Cu(II)] with four 1,2,4-triazole units obtained from 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-methylphenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile (5) in the presence of dimethylaminoethanol and the corresponding anhydrous metal salts is described. The thermal stabilities of the Pc compounds were determined by thermogravimetric analysis. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis.     

Synthesis of some Mannich base derivatives and their antimicrobial activity study

A series of 2-(phenyl)-2-(morpholin-4-yl)-N-phenylacetamide I–VII were synthesized by Mannich base method. Synthesized compounds I–VII were confirmed by IR, ¹H NMR, ¹³C NMR, mass and elemental analyses. Synthesized compounds I–VII were screened for antibacterial activity against various bacterial strains and compared with standard Ciprofloxacin at concentration 100 μg/mL and for antifungal activity against various fungal strains and compared with Clotrimazole at concentration 100 μg/mL; particularly 3-(4-chlorophenyl)-3-(morp holin-4-yl)-N-phenylpropanamide lll that has high antibacterial activity against Streptococcus epidermidis was compared with standard Ciprofloxacin.     

A new triterpene glycoside from sea cucumber Holothuria leucospilota

A new triterpene glycoside, leucospilotaside A, along with a known saponin, isolated from sea cucumber Holothuria leucospilota, and its structure was elucidated as 3β-O-[4-O-sodiumsulfate-β-D-quinovopyranosyl-(1→2)-β-D-xylopyranosyl]-holosta-22-ketone-9-en-17α,25α-diol (1) by extensive spectroscopic analysis and chemical methods. Leucospilotaside A (1) has a ketone carbonyl group (22) in the aglycon side chain.     

A new triterpenoid saponin from the roots of Platycodon grandiflorum

A new triterpenoid saponin, 3-O-β-D-glucopyranosyl 16-oxo-platycodigenin 28-O-β-D-apiofuranosyl-(1→3)-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyra-nosyl ester, was isolated from the roots of Platycodon grandiflorum, together with three known saponins, including platycodin D, deapio platycoside E and platycoside E. The structure of the new compound, named 16-oxo-platycodin D, was elucidated on the basis of spectroscopic data.     

Reactivity of intramolecularly coordinated aluminum compounds to R3EOH (E = Sn,Si). Remarkable migration of N,C,N and O,C,O pincer ligands

The reaction of organoaluminum compounds containing O,C,O or N,C,N chelating (so called pincer) ligands [2,6-(YCH₂)₂C₆H₃]AlⁱBu₂ (Y = MeO 1, ^tBuO 2, Me₂N 3) with R₃SnOH (R = Ph or Me) gives tetraorganotin complexes [2,6-(YCH₂)₂C₆H₃]SnR₃ (Y = MeO, R = Ph 4, Y = MeO, R = Me 5; Y = ^tBuO, R = Ph 6, Y = ^tBuO, R = Me 7; Y = Me₂N, R = Ph 8, Y = Me₂N, R = Me 9) as the result of migration of O,C,O or N,C,N pincer ligands from aluminum to tin atom. Reaction of 1 and 2 with (ⁿBu₃Sn)₂O proceeded in similar fashion resulting in 10 and 11 ([2,6-(YCH₂)₂C₆H₃]SnⁿBu₃, Y = MeO 10; Y = ^tBuO 11) in mixture with ⁿBu₃SnⁱBu. The reaction 1 and 3 with 2 equiv. of Ph₃SiOH followed another reaction path and ([2,6-(YCH₂)₂C₆H₃]Al(OSiPh₃)₂, Y = MeO 12, Me₂N 13) were observed as the products of alkane elimination. The organotin derivatives 4–11 were characterized by the help of elemental analysis, ESI-MS technique, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy and in the case 6 and 8 by single crystal X-ray diffraction (XRD). Compounds 12 and 13 were identified using elemental analysis,¹H, ¹³C, ²⁹Si NMR and IR spectroscopy.     

Synthesis,spectroscopic studies and structures of square-planar nickel(II) and copper(II) complexes derived from 2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol

Two new nickel(II) [Ni(L)₂] and copper(II) [Cu(L)₂] complexes have been synthesized with bidentate NO donor Schiff base ligand (2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol) (HL) and both complexes Ni(L)₂ and Cu(L)₂ have been characterized by elemental analyses, IR, UV–vis, ¹H, ¹³C NMR, mass spectroscopy and room temperature magnetic susceptibility measurement. The tautomeric equilibria (phenol-imine, O–H?N and keto-amine, O?H–N forms) have been systemetically studied by using UV–vis absorption spectra for the ligand HL. The UV–vis spectra of this ligand HL were recorded and commented in polar, non-polar, acidic and basic media. The crystal structures of these complexes have also been determined by using X-ray crystallographic techniques. The complexes Ni(L)₂ and Cu(L)₂ crystallize in the monoclinic space group P2₁/n and P2₁/c with unit cell parameters: a = 10.4552(3) Å and 12.1667(4) Å, b = 8.0121(3) Å and 10.4792(3) Å, c = 13.9625(4) Å and 129.6616(3)Å, V = 1155.22(6) Å³ and 1155.22(6) Å³, D_x = 1.493 and 1.476 g cm^?3 and Z = 2 and 2, respectively. The crystal structures were solved by direct methods and refined by full-matrix least squares to a find R = 0.0377 and 0.0336 of for 2340 and 2402 observed reflections, respectively.     

Stereoselective synthesis and characterization of novel trans-4-(thiophenyl)pyrazolyl-β-lactams and their C–3 functionalization

A stereoselective synthesis and C–3 functionalization of a long series of novel hybrid 4-(thiophenyl)pyrazolyl-β-lactams have been carried out. The divergent substrate scope and mechanistic insights were examined to delineate the generality of reaction that favored trans-β-lactams 4a-q almost exclusively in all cases. The C–3 functionalization was achieved by Lewis acid assisted nucleophilic substitution reaction of cis-3-chloro-β-lactams 6a-e to afford cis-3-monosubstituted-β-lactams 7a-e. The cis stereochemistry of β-lactams 7a-e was further established by stereospecific desulfurization with Raney-nickel, in representative cases (7a,b), leading to the formation of cis-β-lactams 8a,b. The structures and stereochemical assignments for synthesized β-lactams have been unambiguously confirmed using FT-IR, 1D NMR (¹H and ¹³C), 2D NMR (¹H–¹H COSY, ¹H–¹³C HSQC and ¹³C DEPT–135), elemental analysis (CHN), mass spectrometry (ESI-MS) and single crystal X-ray crystallography, in representative cases (4b,e). The cis and trans configuration of the hydrogen/chloro/nucleophile substituent at C–3 was assigned with respect C4–H of the β-lactam ring.     

Functionalized N-heterocyclic carbene iridium complexes: Synthesis,structure and addition polymerization of norbornene

Picolyl, pyridine, and methyl functionalized N-heterocyclic carbene iridium complexes [Cp¹Ir(C^N)Cl]Cl (4, C^N = 3-Methyl-1-picolyimidazol-2-ylidene), [Cp¹Ir(C^N)Cl][Cp¹IrCl₃] (5), [Cp¹Ir(C-N)Cl]Cl (6, C-N = 3-Methyl-1-pyridylimidazol-2-ylidene) and [Cp¹Ir(L)Cl₂] (7, L = 1,3-dimethylimidazol-2-ylidene) have been synthesized by transmetallation from Ag(I) carbene species, and characterized by ¹H NMR, ¹³C NMR spectra and elemental analyses. The molecular structures of 5–7 have been confirmed by X-ray single-crystal analyses. The iridium carbene complexes 4 and 6 show moderate catalytic activities (3.03 × 10⁵ g PNB (mol Ir)^?1 h^?1 and 1.70 × 10⁶ g PNB (mol Ir)^?1 h^?1) for the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as co-catalyst. The produced polynorbornene have been characterized by IR, ¹H NMR and ¹³C NMR spectra, showing it follows the vinyl-addition-type of polymerization.