HPLC profiles and spectroscopic data of cassane-type furanoditerpenoids.

The data presented here are related to the research paper entitled "Hydroxylated furanoditerpenoids from the pupal case produced by the bruchid beetle Sulcobruchus sauteri inside the seed of Caesalpinia decapetala" (Akihara et al., 2018) [1]. In this data article, we provide high-performance liquid chromatography (HPLC) profiles of seven undescribed hydroxylated furanoditerpenoids, caesalsauteolide, 2-hydroxycaesaljapin, 2,7-dihydroxycaesaljapin, 2-hydroxycaesalacetal, caesalsauterol, 6-acetylcaesalsauterol, norcaesalsauterol isolated from the pupal cases produced by Sulcobruchus sauteri and four known compounds, caesaljaponin A (Kamikawa et al., 2015) [2], caesaljaponin B (Kamikawa et al., 2015) [2], caesalacetal (Kamikawa et al., 2016) [3], and caesaljapin (Kamikawa et al., 2016; Ogawa et al., 1992) [3], [4] isolated from the cotyledons of the intact seeds of Caesalpinia decapetala. Besides, 1D NMR, 2D NMR, and HRESIFTMS data of the seven undescribed furanoditerpenoids are also presented.

Specifications table

Value of the data

The data presents HPLC profiles, NMR data, and HRESIMS data of newly isolated furanoditerpenoids and could be used by other researchers.

The provided information on the spectroscopic data of furanoditerpenoids could be useful for the analysis of spectra and determination of the structure of other furanoditerpenoids.

This data can serve as a benchmark for other researchers to elucidate the structures of furanoditerpenoids.

Data

The data set presented in this article focuses on characterization of the cassane-type furanoditerpenoids described in [1]. The article provides the information on the high-performance liquid chromatography (HPLC) profiles and spectroscopic data of the isolated furanoditerpenoids. The HPLC profiles of the furanoditerpenoids 1–4 shown in Fig. 1 isolated from the EtOAc-soluble fraction of the intact seeds of Caesalpinia decapetala are given in Fig. 2 [2], [3], [4]. The HPLC profiles of the furanoditerpenoids 5–11 shown in Fig. 3 isolated from the EtOAc-soluble fraction of the pupal cases produced by Sulcobruchus sauteri are given in Fig. 4. Figs. 5a–g, 6a–g, 7a–g, 8a–g, 9a–g, 10a–g, and 11a–g show 1D NMR, 2D NMR, and HRESIFTMS of the undescribed furanoditerpenoids 5–11. Analyses of the spectra of 5–11 are described in the research article [1].

Fig. 1

Structures of furanoditerpenoids isolated from the intact seeds of C. decapetala.

Fig. 2

HPLC profiles of a) the EtOAc-soluble fraction of the intact seeds of C. decapetala, b) caesaljaponin B (2), c) caesaljaponin A (1), d) caesalacetal (3), and e) caesaljapin (4).

Fig. 3

Structures of furanoditerpenoids isolated from the pupal cases produced by S. sauteri.

Fig. 4

HPLC profiles of a) the EtOAc-soluble fraction of the pupal case produced by S. sauteri, b) norcaesalsauterol (11), c) 2,7-dihydroxycaesaljapin (7), d) caesalsauteolide (5), e) caesalsauterol (9), f) 2-hydroxycaesalacetal (8), g) 6-acetylcaesalsauterol (10), and h) 2-hydroxycaesaljapin (6).

Fig. 5

a.1H NMR (400 MHz, CD3OD) of 5. b.13C NMR and DEPT (100 MHz, CD3OD) of 5. c.1H-1H COSY of 5. d. NOESY of 5. e. HSQC of 5. f. HMBC of 5. g. (+)HRESIFTMS of 5.

Fig. 6

a.1H NMR (400 MHz, CD3OD) of 6. b.13C NMR and DEPT (100 MHz, CD3OD) of 6. c.1H-1H COSY of 6. d. NOESY of 6. e. HSQC of 6. f. HMBC of 6. g. (-)HRESIFTMS of 6.

Fig. 7

a.1H NMR (400 MHz, CD3OD) of 7. b.13C NMR and DEPT (100 MHz, CD3OD) of 7. c.1H-1H COSY of 7. d. NOESY of 7. e. HSQC of 7. f. HMBC of 7. g. (-)HRESIFTMS of 7.

Fig. 8

a.1H NMR (400 MHz, CD3OD) of 8. b.13C NMR and DEPT (100 MHz, CD3OD) of 8. c.1H-1H COSY of 8. d. NOESY of 8. e. HSQC of 8. f. HMBC of 8. g. (+)HRESIFTMS of 8.

Fig. 9

a.1H NMR (400 MHz, CD3OD) of 9. b.13C NMR and DEPT (100 MHz, CD3OD) of 9. c.1H-1H COSY of 9. d. NOESY of 9. e. HSQC of 9. f. HMBC of 9. g. (+)HRESIFTMS of 9.

Fig. 10

a.1H NMR (400 MHz, CD3OD) of 10. b.13C NMR and DEPT (100 MHz, CD3OD) of 10. c.1H-1H COSY of 10. d. NOESY of 10. e. HSQC of 10. f. HMBC of 10. g. (+)HRESIFTMS of 10.

Fig. 11

a.1H NMR (400 MHz, CD3OD) of 11. b.13C NMR and DEPT (100 MHz, CD3OD) of 11. c.1H-1H COSY of 11. d. NOESY of 11. e. HSQC of 11. f. HMBC of 11. g. (+)HRESIFTMS of 11.

Experimental design, materials, and methods

NMR spectra were acquired using a JEOL A400 spectrometer (400 MHz for 1H, 100 MHz for 13C). 1H and 13C NMR chemical shifts were referenced to residual solvent peaks: δH 3.30 (residual CHD2OD) and δC 49.0 for CD3OD. HRESIMS were carried out using a Thermo Fisher Scientific LTQ Orbitrap XL mass spectrometer at the Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University. HPLC-photodiode array (PDA) analyses were performed with an Inertsil ODS-3 column (150×4.6 mm i.d., 5 μm) on a JASCO LC-2000 instrument equipped with a JASCO MD-2015 multiwavelength detector. The solvents, (A) CH3CN and (B) 1% AcOH, were used as the mobile phase in the following gradient elution: 0–5 min, 60% A; 5–45 min, 60–80% A; 45–55 min 80–100% A with a flow rate of 0.6 ml/min.

Furanoditerpenoids 5–11

Methyl (2S,4R,4aS,6aS,7S,11aR,11bR)-1,2,3,4,4a,5,6,7,11,11a-decahydro-2,7-dihydroxy-4,7-dimethyl-12-oxo-6a,11b-(epoxymethano)phenanthro[3,2-b]furan-4-carboxylate (caesalsauteolide) (5)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 5 are shown in Fig. 5a–g.

(2S,4R,4aS,6aS,7R,11aS,11bS)-1,2,3,4,4a,5,6,6a,7,11,11a,11b-Dodecahydro-2-hydroxy-4-(methoxycarbonyl)-4,7-dimethylphenanthro[3,2-b]furan-11b-carboxylic acid (2-hydroxycaesaljapin) (6)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 6 are shown in Fig. 6a–g.

(2S,4R,4aS,6S,6aS,7R,11aS,11bS)-1,2,3,4,4a,5,6,6a,7,11,11a,11b-Dodecahydro-2,6-dihydroxy-4-(methoxycarbonyl)-4,7-dimethylphenanthro[3,2-b]furan-11b-carboxylic acid (2,7-dihydroxycaesaljapin) (7)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 7 are shown in Fig. 7a–g.

Methyl (2R,4R,4aR,5R,6aS,7R,11aS,11bS,12S)-2,3,4,4a,5,6,6a,7,11,11a-decahydro-2,12-dihydroxy-4,7-dimethyl-1H-5,11b-(epoxymethano)phenanthro[3,2-b]furan-4-carboxylate (2-hydroxycaesalacetal) (8)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 8 are shown in Fig. 8a–g.

Methyl (2R,4R,4aR,5R,6aR,11aS,11bS)-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydro-2,5-dihydroxy-11b-(hydroxymethyl)-4-methyl-7-methylenephenanthro[3,2-b]furan-4-carboxylate (caesalsauterol) (9)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 9 are shown in Fig. 9a–g.

Methyl (2R,4R,4aR,5R,6aR,11aS,11bS)-5-acetoxy-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydro-2-hydroxy-11b-(hydroxymethyl)-4-methyl-7-methylenephenanthro[3,2-b]furan-4-carboxylate (6-acetylcaesalsauterol) (10)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 10 are shown in Fig. 10a–g.

Methyl (2R,4R,4aR,5R,6aR,11aS,11bS)-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydro-2,5-dihydroxy-11b-(hydroxymethyl)-4-methyl-7-oxophenanthro[3,2-b]furan-4-carboxylate (norcaesalsauterol) (11)

1D NMR, 2D NMR, and HRESIFTMS spectra of the compound 11 are shown in Fig. 11a–g.

Subject area	Chemistry
More specific subject area	Natural products
Type of data	Figure
How data was acquired	NMR spectroscopy: JEOL A400; HRESIMS: Thermo Fisher Scientific LTQ Orbitrap XL mass spectrometer; High-performance liquid chromatography (HPLC)-photodiode array (PDA) analyses: Inertsil ODS-3 column (150×4.6 mm i.d., 5 μm) on a JASCO LC-2000 instrument equipped with a JASCO MD-2015 multiwavelength detector.
Data format	Analyzed
Experimental factors	The undescribed hydroxylated furanoditerpenoids were purified by column chromatography.
Experimental features	The isolated compounds were characterized by HRESIMS and NMR spectroscopy
Data source location	Higashi-Hiroshima, Japan
Data accessibility	Data are available with this article
Related research article	Y. Akihara, S. Kamikawa, Y. Harauchi, E. Ohta, T. Nehira, H. Ômura, S. Ohta, Hydroxylated furanoditerpenoids from pupal cases produced by the bruchid beetle Sulcobruchus sauteri inside the seeds of Caesalpinia decapetala, Phytochemistry 156 (2018) 151–158.