Diterpenoid acids from <Emphasis Type="Italic">Pinus koraiensis</Emphasis>

Two new diterpenoid acids, pinusenocarp (1) and pinusenoid (2), were isolated from the pine cone of Pinus koraiensis. All the compounds were characterized on the basis of spectral analysis, viz. ¹H NMR, ¹³C NMR, IR, UV, ESI-MS, and elemental analysis.     

A new naphthoquinone and a new neolignan from <Emphasis Type="Italic">Ligularia vellerea</Emphasis> rhizomes

In the course of phytochemical investigations of Ligularia vellerea rhizomes, a new naphthoquinone, 2,5-dihydroxy-6,7-dimethylnaphthoquinone (1), and a new neolignan, 4-[(3',4'-dihydroxycinnamoyl)-oxy]methyl cinnamate (2), have been isolated and characterized on the basis of spectroscopic methods (¹H NMR, ¹³C NMR, 2D NMR, and MS).     

A new 9,10-dihydrophenanthrenedione from <Emphasis Type="Italic">Cannabis sativa</Emphasis>

The structure of a new 9,10-dihydrophenanthrenedione, which was isolated from the leaves and branches of Cannabis sativa L., was elucidated as 9,10-dihydro-2,3,5,6-tetramethoxyphenanthrene-1,4-dione (1) on the basis of MS, ¹H NMR, and ¹³C NMR methods, especially 2D NMR techniques (HMBC and NOESY).     

A new tigliane-type diterpene ester from <Emphasis Type="Italic">Wikstroemia scytophylla</Emphasis>

A new tigliane-type diterpene ester, wiksphyllamin B (1), and one known compound, 12-O-benzoylphorbol 13-octanoate (2), were isolated from the stems of Wikstroemia scytophylla Diels. Their structures were identified using spectroscopic methods. The incorrect assignment of ¹³C NMR data of compound 2 in the literature was revised according to the 2D NMR spectra.     

A new flavonol derivative from <Emphasis Type="Italic">Fagopyrum dibotrys</Emphasis>

A new flavonol derivative 3, 8-dihydroxy-10-methoxy-5-H-isochromeno[4, 3-b]chromen-7-one (1) together with four known compounds, glutinone (2), luteolin (3), acacetin 7-O-α-L-rhamnopyranosyl- (1→6)-β-D-glucopyranoside (4), and rutin (5) were isolated from the dried roots of Fagopyrum dibotrys. Their structures were determined by UV, IR, MS, ¹H, and ¹³C NMR spectroscopic analysis, including 2D NMR. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 567–568, November–December, 2008.     

Two new ceramides from <Emphasis Type="Italic">Zephyranthes candida</Emphasis>

Two new ceramides were isolated from the bulbs of Zephyranthes candida. Their structures were established as (2S,3S,4R,13E)-1,3,4-trihydroxy-2-[(2′R)-2′-hydroxytetracosanoylamino]-13-octadecene, named zephyranamide A (1) and (2S,3S,4R)-1,3,4-trihydroxy-2-octacosanoylaminohexadecene, named zephyranamide B (2). The structures of the new compounds were elucidated by spectral techniques including ¹H NMR, ¹³C NMR, as well as HSQC, HMBC, DEPT, and COSY.     

New flavonoid-<Emphasis Type="Italic">C</Emphasis>-glycosides from <Emphasis Type="Italic">Triticum aestivum</Emphasis>

Two new flavonoid-C-glycosides named triticuside A (1a) and triticuside B (1b) were isolated from bran of Triticum aestivum L. The structures of the two new compounds were elucidated by spectral techniques including ¹H NMR, ¹³C NMR as well as HSQC, HMBC, and COSY. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 135–137, March–April, 2008.     

Spectroscopic characterization and <Emphasis Type="Italic">Ab initio</Emphasis> calculations of new diazaphosphole and diazaphosphorinane

Phosphoryl chloride is used as a starting material to synthesize new diazaphosphole, (1) and diazaphosphorinane, (2). The products are characterized by ¹H, ¹³C, ³¹P NMR, and IR spectroscopy. A high value ² J(PNH) = 17.0 Hz, 17.2 Hz is measured for two non-equivalent NH protons of endocyclic nitrogen atoms in compound 1, while it greatly decreases to 4.5 Hz in 2. Also, great amounts are obtained for two ² J(P,C) as well as two ³ J(P,C) in the ¹³C NMR spectrum of 1, but they are zero in 2. Here, the effect of ring strain and ring size on the structural and spectroscopic parameters is observed. The ³¹P NMR spectra reveal that δ(³¹P) of compound 1 is far much more downfield (12.63 ppm) relative to that of compound 2 (−10.39 ppm). Furthermore, ab initio quantum chemical calculations are performed to optimize the structures of these molecules by density functional theory (B3LYP) and Hartree-Fock (HF) methods, using the standard 6−31+G** basis set. The stabilization energies are calculated by the equation ΔE _{stabilization} = E _molecule − ΣE _i , where i = atom. To obtain the atomic hybridizations, NBO computations are made at the B3LYP/6−31+G** level. Also, by NMR calculations the ¹H, ¹³C, ³¹P chemical shifts are obtained and compared with the experimental ones.     

选择性响应Cu~(2+)、Ag~+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)双(2,1-亚苯基)二乙酸酯(探针1);再将其进一步水解得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)二苯酚(探针2)。经1H NMR、13C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu2+、Ag+不同的荧光猝灭作用,探针2还能识别阴离子F-和AcO-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2∶1。     

Nepetadiol,a new triterpenediol from <Emphasis Type="Italic">Nepeta suavis</Emphasis>

Nepetadiol, a new tetracyclic triterpene diol (1), was isolated from the chloroform-soluble portion of the whole plant of Nepeta suavis. In addition, lawsonin (2) and lawsonic acid (3) have been isolated for the first time from this species. The structures of the isolated compounds were based on ¹H and ¹³C NMR spectra, including two-dimensional NMR techniques like COSY, HMQC, and HMBC, and comparison with the literature data.     

A new alloside from <Emphasis Type="Italic">Neocheiropteris palmatopedata</Emphasis>

A new compound, 2,4,6-trihydroxybenzoic acid 4-O-β-D-allopyranoside (1), together with four known compounds, sucrose (2), fructose (3), ecdysterone (4), and β-sitosterol (5) was isolated from the roots of Neocheiropteris palmatopedata (Baker) Christ. The new compound was identified based on extensive spectroscopic studies including HR-ESI-MS, FAB-MS, ¹H NMR, ¹³C NMR, DEPT, ¹H–¹H COSY, HSQC, HMBC, and NOESY spectra, and the known compounds were identified by their spectroscopic data analysis, comparison with reports in the literature, and co-chromatography with authentic standards. Compounds 2, 3, and 5 were obtained from the Neocheiropteris genus for the first time, and 4 was originally isolated from the plant.     

选择性响应Cu2+、Ag+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）双（2,1-亚苯基）二乙酸酯（探针1）;再将其进一步水解得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）二苯酚（探针2）。经¹H NMR、¹³C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu²⁺、Ag⁺不同的荧光猝灭作用,探针2还能识别阴离子F^-和AcO^-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2：1。     

Three phytoecdysteroids from <Emphasis Type="Italic">Sagina japonica</Emphasis> and potential biotransforming pathways of japonicone

In continuation of the series of studies on the chemical components of the whole plant of Sagina japonica Ohwi, another two phytoecdysteroids named 22,25-epoxy-24-methylene-2,3,14,20-tetrahydrocholest-7-en-6-one, or japonicone (1) and shidasterone (2), along with the previously reported compound 20-hydroxyecdysone (3), have been isolated on the basis of polyspectroscopic methods (¹H NMR, ¹³C NMR, HMQC, HMBC, MS, and IR). The heteronuclear multiple bond coherence (HMBC) data of shidasterone (2) was supplemented for first time. Potential biotransforming pathways of japonicone (1) were discussed.     

Two new coumarins from <Emphasis Type="Italic">Euonymus hamiltonianus</Emphasis>

Two new coumarins, euonidiol (1) and euoniside (2), and a known flavone, luteolin 7-methyl ether, were isolated from the aerial parts of the plant Euonymus hamiltanianus Wall. All the compounds were characterized on the basis of spectral analysis viz. ¹H NMR, ¹³C NMR, DEPT, IR, UV, ESI-MS, and elemental analysis. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 10–11, January–February, 2008.     

Another two novel ceramides from <Emphasis Type="Italic">Zephyranthes candida</Emphasis>

From the the bulbs of Zephyranthes candida (Amaryllidaceae), another two novel ceramides have been isolated and identified. The structures of the two novel compounds were established as (2S,3S,4R,21E,2′R)2-[N-(2′-hydroxynonadecanoyl)-N-(1′′,2′′-dihydroxyethyl)amino]-21-hexacosene-1,3,4-triol, named zephyranamide C (1), and 1,3,4,5,6-pentahydroxy-2-(2′-hydroxyhexacosanoyl-amino)-18-(E)-tetracosene, named zephyranamide D (2). Their structures and stereochemistries were elucidated by spectral techniques including ¹H NMR, ¹³C NMR, as well as HSQC, HMBC, DEPT, and COSY.     

Chemical study of <Emphasis Type="Italic">Petasites albus</Emphasis>

The new benzofurans petalbin (1) and petalbone (2) were isolated from roots of Petasites albus. Their structures were established using physicochemical and spectral (IR, PMR, ¹³C NMR, ¹³C DEPT 135) data.     

New glycosidic and other constituents from hulls of <Emphasis Type="Italic">Oryza sativa</Emphasis>

Three new compounds, 4-hydroxymethylene-7-(9,9,13-trimethylcyclohexyl)-heptanyl-3′,7′,7′-trimethylcyclohexa-2′,4′-dien-1′-oate (1), 1-(n-hexadec-7-enoxy)-6-(n-octadecanoxy)-β-D-glucopyranoside (2), and (Z)-12-hydroxy-9-octadecenoic acid-12-β-D-glucopyranoside (3), along with the known compound hexacosanoic acid (4), were isolated and identified from the rice hulls of Oryza sativa. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹H COSY, ¹H-¹³C HETCOR, DEPT) aided by EIMS, FABMS, HRFABMS, and IR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 344–347, July–August, 2007.     

First optically active <Emphasis Type="Italic">PC</Emphasis>-palladacycle bearing a phosphorus atom in an axially chiral environment

Direct aromatic C—H bond activation in the (S _a)-BINOL-derived phosphite (S _a)-HL afforded the dimeric cyclopalladated complex (S _a,S _a)-{Pd(η²-L)(μ-Cl)}₂ (2) which is the first optically active PC-palladacycle bearing a phosphorus atom in an axially chiral environment. ortho-Palladated structure of dimer 2 was confirmed by spectral (¹H and ³¹P NMR) examination of its mononuclear derivatives and by X-ray diffraction analysis of the phosphine adduct (η²-L)PdCl(PPh₃) (4). The enantiomeric purity of the starting ligand remained unchanged in the PC-palladacycle under the thermal conditions used for the cyclopalladation (∼110 °C); this fact was confirmed by the ³¹P NMR spectroscopy after chiral derivatization in situ of dimer (S _a,S _a)-2 with the (R _C )-valinate chiral auxiliary (Val). trans(N,C)-Configuration of the valinate complex (η²-L)Pd(Val) (5) was established by ¹H NMR and supported by DFT calculations. The chirality transfer in the new PC-palladacycle was discussed on the basis of X-ray diffraction data for the phosphine adduct rac-4 and DFT calculations performed for both phosphine and valinate mononuclear derivatives.     

Facile synthesis of chiral <Emphasis Type="Italic">N</Emphasis>-glycosylated amino acids

Five designed chiral glycosylated amino acids have been synthesized for the first time by coupling of 1,3,4,6-tetra-O-acetyl-β-D-glucosamine sulfate (2), previously prepared by direct acetylation of D-glucosamine hydrochloride with acetic anhydride, with chiral Fmoc-protected amino acids and DIC, HOBt, and DIEA under mild conditions. The structures of these new compounds were characterized by IR, ¹H NMR, and ¹³C NMR spectroscopy and ESI MS.     

Quantitative <Superscript>2</Superscript>H NMR spectroscopy

The selectivity of deuterium distribution between the nonequivalent positions in 3-carene (1), 4-α-acetyl-2-carene (2), and 4-(1-hydroxyethyl)-2-carene (3) has been measured by ²H-{¹H} NMR spectroscopy at the natural abundance of deuterium. These “H/D-isotope portraits” were shown to be typical of terpenes and terpenoids produced in plants via the biosynthetic DXP pathway. The mechanism of acylation of 1 was studied by the density functional theory method (PBE functional, TZ2p basis set). The six-membered ring in compound 1 is planar. However, the endo attack of electrophiles on this ring is more favorable both kinetically and thermodynamically. It was shown both experimentally and theoretically that the elimination of a hydrogen atom in the second reaction step proceeds stereoselectively at the C(2) atom from the anti position with respect to the three-membered ring and occurs with pronounced nucleophilic assistance from the carbonyl group. For Part 2, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1657–1664, August, 2008.