3-Aminofurostane Alkaloids from <i>Solanum paniculatum</i> (“Jurubeba Verdadeira”) Roots

Silva, Tania M. S.; Silva, Telma M. G.; Agra, Maria F.; Camara, Celso A.

doi:10.21577/0103-5053.20190269

Acessibilidade / Reportar erro

Brasil

Journal of the Brazilian Chemical Society

Español English

Brasil

Español English

sumário « anterior atual seguinte »

Sumário

Article • J. Braz. Chem. Soc. 31 (5) • May 2020 • https://doi.org/10.21577/0103-5053.20190269 copy

3-Aminofurostane Alkaloids from Solanum paniculatum (“Jurubeba Verdadeira”) Roots

Authorship SCIMAGO INSTITUTIONS RANKINGS

The roots of Solanum paniculatum (Solanaceae) have extensively been used in folk medicine to treat liver infections and as a diuretic. Ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS/MS) were used for the profiling and structural characterization of alkaloids from the roots of S. paniculatum. Sixteen 3-aminofurostane alkaloids were characterized as novel compounds. In this study, three principal alkaloids were isolated in mixture, and their structures were established by different spectroscopic methods, including 1D, 2D nuclear magnetic resonance (NMR) experiments, and the high-resolution electrospray ionization (HR-ESI)-MS analysis. The isolated alkaloids were used to explore fragmentation pathways. Compound identification was based on the exact mass and fragmentation behaviors. Two compounds were identified as new natural compounds as: (25R)-3β-amino-furost-5-en-22α,26-diol O(26)-β-D-glucopyranoside (fatimagraine) and (25R)-3β-amino-furost-22-en,26-ol O(26)-β-D-glucopyranoside (bhattacharyyaine). The unambiguous assignments of ¹H and ¹³C NMR data and chemical correction of the structure alkaloid jurubine are reported for the first time.

Keywords:
Solanum paniculatum; jurubeba; 3-aminofurostane alkaloids; UPLC-QTOF-MS

	δ_C / ppm	δ_H / ppm (mult., J in Hz)	² J _CH	³ J _CH
1	36.9	1.50 (m), 1.21 (m)	2H-2	3H-19
2	30.0	1.72 (m), 1.12 (m)
3	52.0	2.70 (m)
4	38.7	1.46 (m), 1.03 (m)	H-9	2H-6
5	46.9	1.17 (m)		3H-19
6	31.5	1.75 (m), 1.38 (m)	2H-7
7	32.8	1.70 (m), 0.97 (m)	2H-6
8	36.6	1.58 (m)	2H-7, H-9
9	55.9	0.71 (m)		3H-19
10	38.2		3H-19
11	22.2	1.53 (m), 1.38 (m)	H-9
12	41.2	1.70 (m), 1.11 (m)		3H-18
13	42.3		2H-12, 3H-18	H-20, H-16, 2H-15
14	57.9	1.23 (m)		3H-18
15	32.2	1.95 (ddd, J 12.0, 10.0, 5.0 Hz) 1.24 (m)	H-14, H-16	H-17
16	82.6	4.35 (q, J 7.0 Hz)	2H-15, H-17
17	65.3	1.70 (m)	H-16	3H-18, 3H-21, H-20
18	17.2	0.79 (s)	H-17	H-20
19	12.9	0.85 (s)		2H-1, H-9
20	41.3	2.15 (q, J 7.0 Hz)	3H-21	H-16, 2H-23
21	16.2	0.99 (d, J 7.0 Hz)
22	116.0		H-20, 2H-23	3H-21, 2H-24
23	31.5	1.65 (m), 1.82 (m)	2H-24	H-20, H-25
24	29.1	1.15 (m), 1.62 (m)	H-25	3H-27
25	35.1	1.75 (m)	2H-26, 2H-24, 3H-27
26	76.1	3.72 (dd, J 10.0, 7.0 Hz), 3.37 (dd, J 10.0, 7.0 Hz)	H-25	2H-24, H-1'
27	17.6	0.94 (d, J 7.0 Hz)		2H-24, 2H-26
Glucose
1'	104.7	4.23 (d, J 8.0 Hz)	H-2'	H-3', 2H-26
2'	75.3	3.18 (dd, J 9.0, 8.0 Hz)	H-1', H-3'	H-4'
3'	78.3	3.31 (dd, J 9.0, 8.0 Hz)	H-2'	H-1', H-5'
4'	71.9	3.27 (m)	H-3', H-5'	2H-6'
5'	78.1	3.24 (m)	H-4', 2H-6'	H-3'
6'	62.9	3.85 (dd, J 12.0, 2.0 Hz), 3.65 (dd, J 12.0, 5.0 Hz)	H-5'

Compound	t_R / min	[M + H]⁺ (m/z)	[M + H]⁺ (m/z) calculated	MS/MS fragments (m/z) Tentative identification
1	2.84	626.3898	626.3898	3-amino-dihydroxy-dehydro-furostane-22-ol 608.3860 [M + H - H₂O]⁺, 591.2657 [M + H - H₂O - NH₃]⁺, 573.3530 [M + H - 2H₂O - NH₃]⁺, 464.3369 [M + H - glucose]⁺, 429.3031 [M + H - H₂O - NH₃ - glucose]⁺, 411.2908 [M + H - 2H₂O - NH₃ - glucose]⁺, 393.2814 [M + H - 3H₂O - NH₃ - glucose]⁺, 269.1812 [M + H - 3H₂O - NH₃ - glucose - C₈H₁₂O]⁺
2	2.99	772.4477	772.4477	3-amino-dihydroxy-dehydro-furostane-22-ol-26-di-glucopyranoside 754.4370 [M + H - H₂O]⁺, 610.3963 [M + H - glucose]⁺, 593.3848 [M + H - NH₃ - glucose]⁺, 431.3193 [M + H - NH₃ - 2glucose]⁺, 413.3193 [M + H - H₂O - 2glucose - NH₃]⁺, 395.2957 [M + H - 2H₂O - 2glucose - NH₃]⁺, 377.2877 [M + H - 3H₂O - 2glucose - NH₃]⁺, 281.2274 [M + H - 3H₂O - 2glucose - NH₃ - C₆H₈O]⁺, 271.2069 [M + H - H₂O - 2glucose - NH₃ - C₈H₁₄O₂]⁺, 253.1966 [M + H - 3H₂O - 2glucose - NH₃ - C₈H₁₂O]⁺
3	3.11	774.4634	774.4634	3-amino-dihydroxy-furostane-22-ol-26-di-glucopyranoside 756.4547 [M + H - H₂O]⁺, 738.4454 [M + H - 2H₂O]⁺, 594.4022 [M + H - H₂O - glucose]⁺, 432.3488 [M + H - H₂O - 2glucose]⁺, 415.3056 [M + H - H₂O - 2glucose - NH₃]⁺, 397.3122 [M + H - 2H₂O - 2glucose - NH₃]⁺, 379.2999 [M + H - 3H₂O - 2glucose - NH₃]⁺, 283.2423 [M + H - 3H₂O - 2glucose - NH₃ - C₆H₈O]⁺, 353.1966 [M + H - 3H₂O - 2glucose - NH₃ - C₈H₁₄O]⁺
4	3.22	628.4055	628.4055	3-amino-dihydroxy-furostane-22-ol 610.3965 [M + H - H₂O]⁺, 593.3704 [M + H - H₂O - NH₃]⁺, 575.3593 [M + H - H₂O - NH₃]⁺, 448.3441 [M + H - H₂O - glucose]⁺, 431.3163 [M + H - H₂O - NH₃ - glucose]⁺, 413.3058 [M + H - 2H₂O - NH₃ - glucose]⁺, 395.2949 [M + H - 3H₂O - NH₃ - glucose]⁺, 377.2850 [M + H - 4H₂O - NH₃ - glucose]⁺, 281.2280 [M + H - 4H₂O - NH₃ - glucose - C₆H₈O]⁺, 269.2440 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₄O₂]⁺, 251.1802 [M + H - 4H₂O - NH₃ - glucose - C₈H₁₄O]⁺
5	3.29	774.7634	774.7634	3-amino-dihydroxy-furostane-22-ol-26-di-glucopyranoside 756.4543 [M + H - H₂O]⁺, 738.4458 [M + H - 2H₂O]⁺, 594.4016 [M + H - H₂O - glucose]⁺, 432.2822 [M + H - H₂O - 2glucose]⁺, 415.3064 [M + H - H₂O - 2glucose - NH₃]⁺, 397.3122 [M + H - 2H₂O - 2glucose - NH₃]⁺, 379.2999 [M + H - 3H₂O - 2glucose - NH₃]⁺, 283.2423 [M + H - 3H₂O - 2glucose - NH₃ - C₆H₈O]⁺, 353.1966 [M + H - 3H₂O - 2glucose - NH₃ - C₈H₁₄O]⁺
6	3.58	612.4106	612.4106	3-amino-hydroxy-furostane-22-ol 594.4011 [M + H - H₂O]⁺, 577.3746 [M + H - H₂O - NH₃]⁺, 559.3644 [M + H - 2H₂O - NH₃]⁺, 432.3482 [M + H - H₂O - glucose]⁺, 415.3210 [M + H - H₂O - NH₃ - glucose]⁺, 397.3113 [M + H - 2H₂O - NH₃ - glucose]⁺, 379.3657 [M + H - 3H₂O - NH₃ - glucose]⁺, 383.2972 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 271.2612 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₆O₂]⁺, 253.2489 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₄O]⁺
7	3.90	772.4477	772.4477	3-amino-dihydroxy-dehydro-furostane-22-ol-26-di-glucopyranoside isomer 754.4370 [M + H - H₂O]⁺, 610.3963 [M + H - glucose]⁺, 593.3848 [M + H - NH₃ - glucose]⁺, 431.3193 [M + H - NH₃ - 2glucose]⁺, 413.3193 [M + H - H₂O - 2glucose - NH₃]⁺, 395.2957 [M + H - 2H₂O - 2glucose - NH₃]⁺, 377.2877 [M + H - 3H₂O - 2glucose - NH₃]⁺, 281.2274 [M + H - 3H₂O - 2glucose - NH₃ - C₆H₈O]⁺, 271.2069 [M + H - H₂O - 2glucose - NH₃ - C₈H₁₄O₂]⁺, 253.1966 [M + H - 3H₂O - 2glucose - NH₃ - C₈H₁₂O]⁺
8	4.12	612.4106	612.4106	3-amino-hydroxy-furostane-22-ol isomer 594.4010 [M + H - H₂O]⁺, 577.3746 [M + H - H₂O - NH₃]⁺, 559.3651 [M + H - 2H₂O - NH₃]⁺, 432.3492 [M + H - H₂O - glucose]⁺, 415.3207 [M + H - H₂O - NH₃ - glucose]⁺, 397.3108 [M + H - 2H₂O - NH₃ - glucose]⁺, 379.3657 [M + H - 3H₂O - NH₃ - glucose]⁺, 383.2972 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 271.2612 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₆O₂]⁺, 253.2489 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₄O]⁺
9	4.21	758.4689	758.4685	3-amino-furostane-22-ol-26-di-glucopyranoside 740.4604 [M + H - H₂O]⁺, 578.4096 [M + H - H₂O - glucose]⁺, 417.3568 [M + H - NH₃ - 2glucose]⁺, 416.3518 [M + H - H₂O - 2glucose]⁺, 399.3269 [M + H - H₂O - NH₃ - 2glucose]⁺, 285.2586 [M + H - H₂O - NH₃ - 2glucose - C₆H₈O]⁺, 381.3177 [M + H - 2H₂O - NH₃ - 2glucose]⁺, 255.2120 [M + H - 2H₂O - NH₃ - 2glucose - C₈H₁₄O]⁺
10	4.28	610.3948	610.3949	3-amino-hydroxy-dehydro-furostane-22-ol 592.3856 [M + H - H₂O]⁺, 574.3755 [M + H - 2H₂O]⁺, 430.3345 [M + H - H₂O - glucose]⁺, 413.3070 [M + H - H₂O - NH₃ - glucose]⁺, 395.2962 [M + H - 2H₂O - NH₃ - glucose]⁺, 377.2246 [M + H - 3H₂O - NH₃ - glucose]⁺, 269.2612 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₆O₂]⁺, 251.1813 [M + H - 2H₂O - NH₃ - glucose - C₈H₁₄O]⁺
11	4.54	594.4001	594.4000	(25R)-3β-amino-furost-5-en-22α,26-diol O(26)-β-D-glucopyranoside (fatimagraine) 576.3913 [M + H - H₂O]⁺, 559.3636 [M + H - H₂O - NH₃]⁺, 414.3391 [M + H - H₂O - glucose]⁺, 397.3105 [M + H - H₂O - NH₃ - glucose]⁺, 379.3011 [M + H - 2H₂O - NH₃ - glucose]⁺, 283.2433 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 253.1956 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺
12	4.63	596.4156	596.4156	(25R)-3β-amino-5α-furostane-22α,26-diol O(26)-β-D-glucopyranoside (jurubine) 578.4058 [M + H - H₂O]⁺, 561.3786 [M + H - H₂O - NH₃]⁺, 416.3538 [M + H - H₂O - glucose]⁺, 399.3956 [M + H - H₂O - NH₃ - glucose]⁺, 381.3146 [M + H - 2H₂O - NH₃ - glucose]⁺, 285.2581 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 255.2109 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺
13	4.79	756.4528	756.4528	3-amino-dehydro-furostane-22-ol-26-di-glucopyranoside 738.4423 [M + H - H₂O]⁺, 594.4001 [M + H - glucose]⁺, 577.3755 [M + H - NH₃ - glucose]⁺, 559.3644 [M + H - H₂O - NH₃ - glucose]⁺, 432.3481 [M + H - 2glucose]⁺, 414.3373 [M + H - H₂O - 2glucose]⁺, 413.3075 [M + H - NH₃ - 2glucose]⁺, 397.3119 [M + H - H₂O - NH₃ - glucose]⁺, 253.1961 [M + H - 2H₂O - NH₃ - 2glucose - C₈H₁₄O]⁺
14	5.08	594.4001	594.4000	fatimagraine isomer 576.3906 [M + H - H₂O]⁺, 559.3669 [M + H - H₂O - NH₃]⁺, 414.3371 [M + H - H₂O - glucose]⁺, 397.3110 [M + H - H₂O - NH₃ - glucose]⁺, 379.3002 [M + H - 2H₂O - NH₃ - glucose]⁺, 283.1955 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 253.1955 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺
15	5.17	596.4156	596.4156	jurubine isomer 578.4072 [M + H - H₂O]⁺, 561.3793 [M + H - H₂O - NH₃]⁺, 416.3518 [M + H - H₂O - glucose]⁺, 399.3274 [M + H - H₂O - NH₃ - glucose]⁺, 381.3143 [M + H - 2H₂O - NH₃ - glucose]⁺, 285.2583 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 255.2118 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺
16	6.04	576.3894	576.3894	dehydro-bhattacharyyaine 559.3630 [M + H - NH₃]⁺, 397.3109 [M + H - NH₃ - glucose]⁺, 414.2479 [M + H - glucose]⁺, 379.3002 [M + H - H₂O - NH₃ - glucose]⁺, 283.2439 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 253.1955 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺
17	6.15	578.4051	578.4051	(25R)-3β-amino-furost-22-en,26-ol O(26)-β-D-glucopyranoside (bhattacharyyaine) 561.3789 [M + H - NH₃]⁺, 399.3263 [M + H - NH₃ - glucose]⁺, 416.3539 [M + H - glucose]⁺, 381.3161 [M + H - H₂O - NH₃ - glucose]⁺, 285.2591 [M + H - 2H₂O - NH₃ - glucose - C₆H₈O]⁺, 255.2121 [M + H - 2H₂O - NH₃ - glucose - C₆H₁₆O₂]⁺

	δ_C / ppm	δ_H / ppm (mult., J in Hz)	² J _CH	³ J _CH
1	41.1	1.76 (m), 1.45 (m)		3H-19
2	29.0	1.30 (m), 1.70 (m)
3	51.8	3.31 (m)
4	40.8	2.18 (m)	H-9
5	140.0			3H-19
6	124.3	5.35 (d, J 4.5 Hz)
7	32.8	1.94 (m), 1.28 (m)
8	35.2	1.56 (m)
9	51.6	0.96 (m)		3H-19
10	37.9		3H-19
11	22.1	1.56 (m), 1.30 (m)	H-9
12	42.2	1.70 (m), 1.13 (m)		3H-18
13	41.9		3H-18
14	57.5	1.23 (m)		3H-18
15	33.3	1.97 (m), 1.25 (m)		H-17
16	82.5	4.36 (m)	2H-15, H-17
17	65.9	1.75 (m)	H-16	3H-18, 3H-21
18	16.9	0.83 (s)
19	19.8	1.06 (s)		H-9
20	41.3	2.17 (m)	3H-21
21	16.3	0.98 (d, J 7.0 Hz)		H-20
22	114.0			3H-21
23	31.5	1.81 (m), 1.65 (m)		H-25
24	28.8	1.20-1.40 (m)	H-25	3H-27
25	35.1	1.72 (m)	3H-27
26	76.1	3.73 (m) 3.35 (m)		H-1'
27	17.4	0.95 (d, J 7.0 Hz)		2H-24, 2H-26
Glucose
1'	104.7	4.23 (d, J 8.0 Hz)	H-2'	H-3', 2H-26
2'	75.3	3.13 (m)	H-1', H-3'	H-4'
3'	78.3	3.38 (m)		H-1', H-5'
4'	71.9	3.28 (m)	H-5'	2H-6'
5'	78.0	3.26 (m)	H-4', 2H-6'	H-3'
6'	62.9	3.86 (dd, J 12.0, 2.0 Hz) 3.65 (m)

	δ_C / ppm	δ_H / ppm (mult., J in Hz)	² J _CH	³ J _CH
1	36.9	1.50 (m), 1.21 (m)	2H-2	3H-19
2	30.0	1.72 (m), 1.12 (m)
3	52.0	2.70 (m)
4	38.7	1.46 (m), 1.03 (m)	H-9	2H-6
5	46.9	1.17 (m)		3H-19
6	31.5	1.75 (m), 1.38 (m)	2H-7
7	32.8	1.70 (m), 0.97 (m)	2H-6
8	36.6	1.58 (m)	2H-7, H-9
9	55.9	0.71 (m)		3H-19
10	38.2		3H-19
11	22.2	1.53 (m), 1.38 (m)	H-9
12	41.2	1.70 (m), 1.11 (m)		3H-18
13	44.7		3H-18	H-16, 2H-15
14	56.2	1.23 (m)		3H-18
15	32.2	1.95 (ddd, J 12.0, 10.0, 5.0 Hz), 1.65 (m)	H-14, H-16	H-17
16	85.8	4.70 (dt, J 8.0, 2.0 Hz)	2H-15, H-17
17	65.3	2.44 (d, J 7.5 Hz)	H-16	3H-18, 3H-21
18	14.9	0.69 (s)	H-17
19	12.9	0.85 (s)		2H-1, H-9
20	104.8		H-17	3H-21
21	12.0	1.58 (s)
22	153.0			H-17
23	32.2	1.81 (m), 1.65 (m)		H-25
24	29.1	1.15 (m), 1.62 (m)	H-25	3H-27
25	35.1	1.75 (m)	2H-26, 2H-24, 3H-27
26	76.1	3.72 (dd, J 10.0, 7.0 Hz), 3.37 (dd, J 10.0, 7.0 Hz)	H-25	2H-24, H-1'
27	17.6	0.94 (d, J 7.0 Hz)		2H-24, 2H-26
Glucose
1'	104.7	4.23 (d, J 8.0 Hz)	H-2'	H-3', 2H-26
2'	75.3	3.18 (dd, J 9.0, 8.0 Hz)	H-1', H-3'	H-4'
3'	78.3	3.31 (dd, J 9.0, 8.0 Hz)	H-2'	H-1', H-5'
4'	71.9	3.27 (m)	H-3', H-5'	2H-6'
5'	78.0	3.24 (m)	H-4', 2H-6'	H-3'
6'	62.9	3.85 (dd, J 12.0, 2.0 Hz), 3.65 (dd, J 12.0, 5.0 Hz)	H-5'

Sociedade Brasileira de Química Instituto de Química - UNICAMP, Caixa Postal 6154, 13083-970 Campinas SP - Brazil, Tel./FAX.: +55 19 3521-3151 - São Paulo - SP - Brazil
E-mail: office@jbcs.sbq.org.br

Acompanhe os números deste periódico no seu leitor de RSS

[1] *e-mail: tania.sarmento@ufrpe.br, sarmentosilva@gmail.com