Pestalafuranone A

.

  Pestalafuranone A (1).

Figure 2. Structures of compounds 1–5.

.

 

Table 1. ¹H-NMR Data for 1–3, 5 in CDCl₃ and 4 in acetone-d₆.

Position	1 a	2 a	3 a	4 a	5 a
5	4.65, s	4.85, s	4.63, s	4.78, s	4.78, d (17)
					4.71, d (17)
6	6.10, d (16)	6.26, d (16)	2.45, t (7.5)	6.24, d (16)	2.61, t (7.5)
7	6.86, m	6.97, m	1.52, m	6.85, m	1.55, m
8	1.86, d (7.0)	1.89, d (6.7)	0.93, t (7.5)	1.81, d (6.5)	0.94, t (7.5)
9	2.70, m	6.77, d (16)	2.67, br s	2.90, dd (15, 3.6)	2.86, dd (12, 4.0)
				2.65, dd (15, 6.0)	2.44, dd (12, 7.0)
10	2.70, m	6.04, dd (16, 7.7)	2.67, br s	2.77, m	2.75, ddd (7.0, 4.0, 2.0)
11		4.52, m		2.85, dq (4.5, 2.0)	2.81, dq (7.5, 2.0)
11-OH		1.75, br s
12	2.18, s	1.68, d (7.0)	2.19, s	1.24, d (4.5)	0.93, d (7.5)

Table 2. ¹³C-NMR data for 1–3, 5 in CDCl₃ and 4 in acetone-d₆.

Position	1 a		2 a		3 a		4 a		5 a
2	172.9, qC		173.0, qC		177.5, qC		173.0, qC		174.5, qC
3	123.3, qC		122.7, qC		127.9, qC		123.9, qC		128.7, qC
4	156.6, qC		149.4, qC		158.9, qC		156.3, qC		158.5, qC
5	70.8, CH2		68.6, CH2		71.2, CH2		71.7, CH2		71.8, CH2
6	118.1, CH		118.7, CH		25.6 CH2		119.9, CH		25.6, CH2
7	133.0, CH		134.3, CH		20.6 CH2		132.3, CH		21.4, CH2
8	19.3, CH3		19.6, CH3		13.9, CH3		17.4, CH3		13.9, CH3
9	20.4, CH2		118.6, CH		21.3, CH2		30.2, CH2		29.9 CH2
10	41.0, CH2		140.8, CH		41.3, CH2		57.2, CH		56.8, CH
11	206.1, qC		68.3, CH		206.0, qC		54.7, CH		54.5, CH
12	29.8, CH3		23.5, CH3		29.8, CH3		19.1, CH3		17.2, CH3

Extraction and Isolation

The fermented material was freeze-dried and extracted with methyl ethyl ketone (3 × 500 mL), and the organic solvent was evaporated to dryness under vacuum to afford 5.0 g of crude extract. The extract was fractionated by silica gel column chromatography (5 × 40 cm) using CHCl₃–CH₃OH gradient elution. The fraction (50 mg) that was eluted with 1% MeOH was further separated by semipreparative reversed-phase HPLC (Kramosil C₁₈ column; 10-µm; 10 × 250 mm, 2 mL/min) to afford pestalafuranone B (2; 1.9 mg, t_R 15.3 min; 50% MeOH in H₂O over 2 min, 50–72% over 10 min, 72–74% over 13 min). The fraction (180 mg) that was eluted with 2% MeOH was then separated by Sephadex LH-20 column chromatography (CH₂Cl₂–n-C₆H₁₄ = 4:1) to afford six fractions. Fraction 3 (60 mg) was successively separated by semipreparative reversed-phase HPLC (32% MeOH in H₂O over 2 min, 32–55% over 60 min) afforded pestalafuranones A (1; 1.6 mg, t_R 25.7 min), C (3; 6.0 mg, t_R 26.6 min), D (4; 1.5 mg, t_R 30.0 min), and E (5; 3.5 mg, t_R 31.5 min).
Pestalafuranone A (1): colorless oil; UV (CH₃OH) λ_max 272 (ε 7800), 265 (ε 6600) nm; IR (Neat) ν_max 2962, 1748, 1717, 1448, 1364 cm⁻¹; ¹H- and ¹³C-NMR data, see Table 1 and Table 2; HRESIMS obsd. m/z 217.0840 [M+Na]⁺ (calcd for C₁₁H₁₄O₃Na, 217.0835).


Pestalafuranone B (2): pale yellow oil; [α]_D −16 (c 0.05, CH₃OH); UV (CH₃OH) λ_max 270 (ε 3300) nm; IR (Neat) ν_max 3403 (br), 2932, 1749, 1446 cm⁻¹; ¹H- and ¹³C-NMR data, see Table 1 and Table 2; HRESIMS obsd. m/z 217.0842 [M+Na]⁺ (calcd for C₁₁H₁₄O₃Na, 217.0835).
Pestalafuranone C (3): pale yellow oil; UV (CH₃OH) λ_max 265 (ε 6600), 235 (ε 4300) nm; IR (Neat) ν_max 2919, 1752, 1717, 1445, 1365 cm⁻¹; ¹H- and ¹³C-NMR data, see Table 1 and Table 2; HRESIMS obsd. m/z 219.0998 [M+Na]⁺ (calcd for C₁₁H₁₆O₃Na, 219.0992).
Pestalafuranone D (4): colorless oil; [α]_D +32 (c 0.05, CH₃OH); UV (CH₃OH) λ_max 275 (ε 4460) nm; IR (Neat) ν_max 2963, 1751, 1450, 1381 cm⁻¹; ¹H- and ¹³C-NMR data, see Table 1 and Table 2; HRESIMS obsd. m/z 217.0846 [M+Na]⁺ (calcd for C₁₁H₁₄O₃Na, 217.0835).
Pestalafuranone D (5): colorless oil; [α]_D +16 (c 0.05, CH₃OH); UV (CH₃OH) λ_max 275 (ε 6270) nm; IR (Neat) ν_max 2931, 1753, 1446, 1346 cm⁻¹; ¹H- and ¹³C-NMR data, see Table 1 and Table 2; HRESIMS obsd. m/z 219.0995 [M+Na]⁺ (calcd for C₁₁H₁₆O₃Na, 219.0992).

 SEE

 http://www.mdpi.com/1420-3049/17/12/14015/htm

Molecules 2012, 17(12), 14015-14021; doi:10.3390/molecules171214015

Article

New Furanones from the Plant Endophytic Fungus Pestalotiopsis besseyi

Haitao Liu ¹, Shuchun Liu ^2,3, Liangdong Guo ³, Yonggang Zhang ⁴, Langjun Cui ⁵ and Gang Ding ^1,*

¹

Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100193, China

²

Graduate School of Chinese Academy of Sciences, Beijing 100086, China

³

Institute of Microbiology, Beijing 100086, China

⁴

Biotechnology Center of Shandong Academy of Sciences, Jinan 250014, Shandong, China

⁵

College of Life Science, Shaanxi Normal University, Xi’an 710062, Shaanxi, China

*

Author to whom correspondence should be addressed; Email: Tel.: +86-010-5783-3281; Fax: +86-010-5783-3290.

Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100193, China










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