1H and 13C assignments of two new triterpenes from Cladocolea grahami

The structure elucidation and 1H and 13C assignments of the new triterpenes 3beta-palmitoxy-7beta-hydroxyolean-12-ene (1) and its hydrolysis product 3beta,7beta-dihydroxyolean-12-ene (2) and 3beta-sn-glyceroyl-(1'-palmitoxy)urs-12-ene (3), isolated from the aerial parts of Cladocolea grahami (Loranthaceae), are reported.     

Complete 1H and 13C data assignments of two new guaianolides isolated from Ainsliaea fragrans

Two new guaianolides, 8alpha-hydroxy-11alpha,13-dihydroglucozaluzanin C and 11alpha,13-dihydroglucozaluzanin C, were isolated from Ainsliaea fragrans, along with two known guaianolides, 8alpha-hydroxy-11alpha,13-dihydrozaluzanin C and glucozaluzanin C. The structures of the new compounds were unambiguously established by HR-ESI-MS, one-dimensional (1D) (DEPT), two-dimensional (2D) ((1)H-(1)H COSY, HSQC, HMBC, ROESY) NMR experiments and by comparison with structurally related compounds. The known compounds were identified by comparison of spectral data with published references. Some NMR data of the known compounds were reported for the first time.     

Complete 1H and 13C NMR assignments of clerodane diterpenoids of Salvia splendens

Unambiguous and complete assignments of 1H and 13C NMR chemical shifts for five clerodane diterpenes, four of them isolated from Salvia splendens (salviarin, splendidin and splenolides A and B) and one obtained by acetylation of splenolide A, are presented. The assignments are based on 2D shift-correlated [1H,1H-COSY, 1H,13C-gHSQC-1J(C,H) and 1H,13C-gHMBC-nJ(C,H) (n=2 and 3)] and nuclear Overhauser effect (NOE) experiments. The conformation of the rings of these compounds is supported by the 3J(H,H) values and NOE results.     

Complete assignments of (1)H and (13)C NMR data for two 3beta,8beta-epoxymexicanolides from the fruit of a Chinese mangrove Xylocarpus granatum

Three 3beta,8beta-epoxymexicanolides, including xyloccensin K, 6-acetoxycedrodorin and a new one named xyloccensin W, were isolated from the fruit of a Chinese mangrove Xylocarpus granatum. Their structures were determined by spectroscopic analyses. The first complete assignment of (1)H and (13)C NMR data for xyloccensin W was achieved by means of 2D NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra. In addition, the confusion of (1)H and (13)C NMR data previously reported for xyloccensin K was clarified.     

Complete assignments of the 1H and 13C NMR spectra of five rearranged abietane diterpenoids

An NMR study of five highly functionalized and rearranged abietane diterpenoids is described. In addition to 1D NMR methods, including 1D NOESY spectra, 2D shift‐correlated experiments [¹H, ¹³C‐gHSQC‐¹J (C,H) and ¹H, ¹³C‐gHMBC‐ⁿJ (C,H) (n = 2 and 3)] were used for the complete and unambiguous ¹H and ¹³C chemical shift assignments of these substances. Copyright © 2002 John Wiley & Sons, Ltd.     

1H and 13C NMR spectral assignments of some natural abietane diterpenoids

An NMR study of 11 naturally occurring abietane diterpenoids is described. In addition to one‐dimensional NMR methods, including DPFGSE 1D‐NOE spectra, two‐dimensional shift‐correlated experiments [¹H,¹H COSY, ¹H,¹³C‐gHSQC ¹J(C,H) and ¹H,¹³C‐gHMBC ⁿJ(C,H) (n = 2 and 3)] were used for the complete and unambiguous ¹H and ¹³C chemical shift assignments of these substances. Copyright © 2003 John Wiley & Sons, Ltd.     

Two isomeric epoxysitosterols from Rhododendron formosanum: 1H and 13C NMR chemical shift assignments

1H and 13C NMR assignments of the two isomeric epoxysitosterols, 5,6 alpha-epoxy-5 alpha-stigmastan-3 beta-ol (1) and 5,6 beta-epoxy-5 beta-stigmastan-3 beta-ol (2), isolated from the leaves of Rhododendron formosanum Hemsl were achieved by 1D and 2D techniques such as DEPT, HMBC, HMQC, COSY and NOESY.     

Complete and unambiguous assignments of 1H and 13C chemical shifts of new arylamino derivatives of ortho-naphthofuranquinones

Six new nor-beta-lapachones have been synthesized from reaction of 3-bromo-nor-beta-lapachone with arylamines. These derivatives have potent anticancer properties against several cell lines. Here, we report complete unambiguous assignments of (1)H and (13)C chemical shifts of the new compounds. The assignments were made using a combination of one- and two-dimensional NMR techniques ((1)H, (13)C, (1)H-(1)H COSY, (1)H-(13)C HSQC, and (1)H-(13)C HMBC).     

Structural determination of 3beta-stearyloxy-urs-12-ene from Maytenus salicifolia by 1D and 2D NMR and quantitative 13C NMR spectroscopy

Six pentacyclic triterpenoids, 3beta-stearyloxy-urs-12-ene (1), friedelin (2), 3beta-friedelinol (3), alpha-amyrin (4), beta-amyrin (5), and lupeol (6), have been isolated from the hexane extract of Maytenus salicifolia Reissek (Celastraceae) leaves. The molecular and structural formula as well as the stereochemistry of a new pentacyclic triterpene (1) were determined using data obtained from 1H and 13C NMR spectra, DEPT135 and by 2D HSQC, HMBC, COSY and NOESY experiments. The molecular formula C48H84O2 was established using quantitative 13C NMR, and the molecular weight (692 Da) was confirmed by elemental analysis and mass spectrometry (GC-MS).     

Complete 1H and 13C NMR assignments of two phytosterols from roots of Piper nigrum

Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time.     

1H and 13C NMR assignments for two lignans from the heartwood of Streblus asper

In our ongoing investigation of the bioactive constituents from plants, two new lignans, magnolignan A-2-O-beta-D-glucopyranoside and strebluslignanol were isolated from heartwood of Streblus asper, along with three known lignans, magnolignan A, magnolol, and magnaldehyde D. 1D and 2D NMR experiments, including COSY, HMQC, and HMBC, and other spectroscopic methods, including UV, IR, and MS were used for the determination of the structures and NMR assignments. Primary bioassays showed that magnolignan A-2-O-beta-D-glucopyranoside and strebluslignanol have medium cytotoxic activity against HEp-2 and HepG2 cells, with IC(50) of 13.3 microM, 46.4 microM and 10.1 microM, 21.7 microM, respectively.     

Complete assignments of NMR data of 13 hydroxymethoxyflavones

Diosmetin, 5,7,3'-trihydroxy-4'-methoxyflavone shows chemopreventive, antimutagenic, and antiallergic effects. On the other hand, chrysoeriol, 5,7,4'-trihydroxy-3'-methoxyflavone induced nodABC-lacZ in Rhizobium meliloti. Both of them belong to hydroxymethoxy- flavones. One major difference between diosmetin and chrysoeriol is the substituted position of hydroxyl and methoxyl groups. In order to elucidate the relationships between their structures and activity, one of the first things to be done is the determination of their structures. However, most flavones occur widely in nature, and thus it is difficult to obtain in sufficient amounts from natural sources to identify their structures. Assignments of NMR data of several hydroxymethoxyflavones may help us to identify novel flavonoid compounds isolated from natural sources based on their NMR experiments. Therefore, we report here the complete assignments of 1H and 13C NMR data of 13 hydroxymethoxyflavones.     

Complete 1H and 13C NMR assignments of three labdane diterpenoids isolated from Leonotis ocymifolia and six other related compounds

Unambiguous and complete assignments of ¹H and ¹³C NMR chemical shifts for three structurally complex labadane diterpenoids isolated from Leonotis ocymifolia (leonotin, leonotinin and nepetaefolin) and six other related compounds (hispanolone, 7α‐ and 7β‐hispanols, marrubiin, villenol and andalusol), previously isolated from Labiatae species, are presented. The assignments are based on 2D shift‐correlated [¹H, ¹H‐COSY, ¹H, ¹³C‐gHSQC–¹J(C,H), ¹H,¹³C‐gHMBC–ⁿJ(C,H) (n = 2 and 3)] and DPFGSE 1D‐NOE experiments. Copyright © 2003 John Wiley & Sons, Ltd.     

1H and 13C NMR spectral assignments and conformational analysis of 14 19-nor-neoclerodane diterpenoids

Unambiguous and complete assignments of 1H and 13C NMR chemical shifts for 14 19-nor-neoclerodane diterpenoids, nine of them isolated from natural sources and five other synthetic derivatives, are presented. The assignments are based on 2D shift-correlated (1H,1H-COSY, 1H,13C-gHSQC and 1H,13C-gHMBC) and NOE experiments. The conformations of rings A and B of these compounds are supported by the 3J(H,H) values and they agree with the low-energy conformations obtained by semi-empirical calculations. Moreover, the data obtained in this work for 2-acetoxyteucvidin and a semisynthetic 18-aldehyde derivative indicate that the configuration at C-2 of the former and at C-10 of the latter must be reversed with respect to those reported previously.     

Complete assignments of 1H and 13C NMR data for ten phenylpiperazine derivatives

Ten phenylpiperazine derivatives were designed and synthesized. The first complete assignments of (1)H and (13)C NMR chemical shifts for these phenylpiperazine derivatives were achieved by means of 1D and 2D NMR techniques, including (1)H-(1)H COSY, HSQC and HMBC spectra.     

1H and 13C NMR spectral assignment of androstane derivatives

(1)H and (13)C NMR spectroscopic data for 5alpha-androstanes and halo-5alpha-androstanes with different substituents at positions C-3, C-9, C-11 and C-17 were examined and assigned by a combination of 1D and 2D NMR experiments. The substituent effects on the (13)C chemical shifts were compared with those of epi-androsterone, used as a reference compound. The coupling constants (n)J((19)F,(13)C) were measured for compounds 6, 8, 11 and 14.     

Complete assignments 1H and 13C NMR spectral data of four anabaseine derivatives

The anabaseine derivatives 6-methoxy-7-hydroxy-1-(pyridin-3-yl)-3,4-dihydroisoquinoline, 6,7-dimethoxy-1-(pyridin-3-yl)-1,2,3,4-tetrahydroisoquinoline and 6,7-dimethoxy-1-(piperidin-3-yl)-1,2,3,4-tetrahydroisoquino- line were prepared either by demethylation with HBr or by reduction with different reagents, NaBH4 and H2/PtO2 from 6,7-dimethoxy-1-(pyridin-3-yl)-3,4-dihydroisoquinoline, as starting material. The structures have been fully assigned by the combination of one- and two-dimensional experiments.     

Complete 1H and 13C assignments of some epipodophyllotoxin derivatives

The complete analyses of the ¹H and ¹³C NMR spectra of the ortho ester analogues of etoposide are reported and differentiation of the α and β isomers of these derivatives is suggested by using the γ‐gauche effect upon the ¹³C chemical shift. Copyright © 2003 John Wiley & Sons, Ltd.     

Three New Diterpenoids from Euphorbia wallichii

Three new abietane diterpene lactones, 3α-hydroxyjolkinolide A (1), ent-8α, 14β-dihydroxy-13(15)-ene-16(12α)-abietanolide (2) and ent-8α,14α-dihydroxy-13(15)-ene-16(12α)-abietanolide (3) as well as a known abietane diterpene jolkinolide A (4) were isolated from the roots of Euphorbia wallichii. Their structures were elucidated on the basis of spectroscopic analysis.     

Complete (1)H and (13)C NMR assignments of two new trans-clerodane diterpenoids from Otostegia limbata

Two new tricyclic trans-clerodane diterpenoids trivially named as ballotenic acid A (1) and ballodiolic acid A (2) have been isolated from ethyl acetate fraction of Otostegia limbata. The structure assignments are based on (1)H and (13)C NMR spectra, 2D NMR (HMQC, HMBC, COSY, NOESY and NOE) techniques and comparison with the literature data.