Eight new hydroquinone derivatives, gliomastins A-D (1-4), 9-O-methylgliomastin C (5), acremonin A 1-O-β-D-glucopyranoside (6), gliomastin E 1-O-β-D-glucopyranoside (7), and 6′-O-acetyl-isohomoarbutin (8), together with seven known analogues were isolated from the marine-derived fungus Gliomastix sp. Their structures were elucidated by extensive spectroscopic analysis including 1D and 2D NMR measurements aided by DFT NMR calculations as well as MS data. TDDFT-ECD and OR calculations were performed to determine the absolute configurations of 1 and the aglycones of 6 and 7. Compound 1 features a novel skeleton, biogenetically derived from a Diels-Alder reaction between derivatives of 11 and 13. Compound 2 represents a rare sulfur-containing alkaloid derived from the known hydroquinone 13. Compounds 1, 10 and 12 showed strong cytotoxicity against the L5178Y mouse lymphoma cell line with IC50 values of 1.8, 1.0 and 1.1 μM, respectively. Compound 3 exhibited moderate antitubercular activity against Mycobacterium tuberculosis with a MIC value of 12.5 μM.

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6	C7	C8	C9	C10	C11
1	bDGlcp	102.1	75.0	77.9	71.4	78.2	62.6
	Subst	146.6	118.2	116.2	147.2	132.8	129.8	36.8	48.9	146.8	110.6	20.4


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6	H7	H8	H9	H10	H11	H12	H13
1	bDGlcp	4.88	3.36	3.42	3.26	3.37	3.69-3.89
	Subst	-	6.69	6.54	-	-	-	3.55	2.87	3.99	-	4.84	4.78	1.78


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6	C7/H7	C8/H8	C9/H9	C10/H10	C11/H11	C12/H12	C13/H13
1	bDGlcp	102.1/4.88	75.0/3.36	77.9/3.42	71.4/3.26	78.2/3.37	62.6/3.69-3.89
	Subst	NMR TSV error 2: unequal length of 13C and 1H datasets

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

C=C(C)[C@H]1Cc2c(O[C@@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@H]3O)ccc(O)c21

338.356 g/mol (C₁₇H₂₂O₇)

Eight new hydroquinone derivatives, gliomastins A-D (1-4), 9-O-methylgliomastin C (5), acremonin A 1-O-β-D-glucopyranoside (6), gliomastin E 1-O-β-D-glucopyranoside (7), and 6′-O-acetyl-isohomoarbutin (8), together with seven known analogues were isolated from the marine-derived fungus Gliomastix sp. Their structures were elucidated by extensive spectroscopic analysis including 1D and 2D NMR measurements aided by DFT NMR calculations as well as MS data. TDDFT-ECD and OR calculations were performed to determine the absolute configurations of 1 and the aglycones of 6 and 7. Compound 1 features a novel skeleton, biogenetically derived from a Diels-Alder reaction between derivatives of 11 and 13. Compound 2 represents a rare sulfur-containing alkaloid derived from the known hydroquinone 13. Compounds 1, 10 and 12 showed strong cytotoxicity against the L5178Y mouse lymphoma cell line with IC50 values of 1.8, 1.0 and 1.1 μM, respectively. Compound 3 exhibited moderate antitubercular activity against Mycobacterium tuberculosis with a MIC value of 12.5 μM.

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6	C7	C8	C9	C10	C11
1	bDGlcp	104.1	75.0	78.2	71.5	78.0	62.7
	Subst	148.6	116.8	115.4	151.0	136.9	131.4	36.3	82.2	48.4	26.0	20.0


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6	H7	H8	H9	H10	H11	H12
1	bDGlcp	4.69	3.41	3.42	3.35	3.32	3.68-3.87
	Subst	-	6.80	6.50	-	-	-	3.23	3.70	3.99	-	1.36	1.20


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6	C7/H7	C8/H8	C9/H9	C10/H10	C11/H11	C12/H12
1	bDGlcp	104.1/4.69	75.0/3.41	78.2/3.42	71.5/3.35	78.0/3.32	62.7/3.68-3.87
	Subst	NMR TSV error 2: unequal length of 13C and 1H datasets

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

CC1(C)c2c(O)ccc(O[C@@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@H]3O)c2C[C@@H]1O

356.371 g/mol (C₁₇H₂₄O₈)

Eight new hydroquinone derivatives, gliomastins A-D (1-4), 9-O-methylgliomastin C (5), acremonin A 1-O-β-D-glucopyranoside (6), gliomastin E 1-O-β-D-glucopyranoside (7), and 6′-O-acetyl-isohomoarbutin (8), together with seven known analogues were isolated from the marine-derived fungus Gliomastix sp. Their structures were elucidated by extensive spectroscopic analysis including 1D and 2D NMR measurements aided by DFT NMR calculations as well as MS data. TDDFT-ECD and OR calculations were performed to determine the absolute configurations of 1 and the aglycones of 6 and 7. Compound 1 features a novel skeleton, biogenetically derived from a Diels-Alder reaction between derivatives of 11 and 13. Compound 2 represents a rare sulfur-containing alkaloid derived from the known hydroquinone 13. Compounds 1, 10 and 12 showed strong cytotoxicity against the L5178Y mouse lymphoma cell line with IC50 values of 1.8, 1.0 and 1.1 μM, respectively. Compound 3 exhibited moderate antitubercular activity against Mycobacterium tuberculosis with a MIC value of 12.5 μM.

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6	C7
1,6	Ac	172.7	20.7
1	bDGlcp	104.3	75.1	78.0	71.7	75.2	64.7
	Subst	150.4	119.2	113.7	153.8	118.8	131.0	16.7


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6	H7
1,6	Ac	-	2.03
1	bDGlcp	4.66	3.43	3.44	3.35	3.51	4.25-4.37
	Subst	-	6.92	6.52	-	6.58	-	2.21


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6	C7/H7
1,6	Ac		20.7/2.03
1	bDGlcp	104.3/4.66	75.1/3.43	78.0/3.44	71.7/3.35	75.2/3.51	64.7/4.25-4.37
	Subst		119.2/6.92	113.7/6.52		118.8/6.58		16.7/2.21

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

CC(=O)OC[C@H]1O[C@@H](Oc2ccc(O)cc2C)[C@H](O)[C@@H](O)[C@@H]1O

328.317 g/mol (C₁₅H₂₀O₈)

Eight new hydroquinone derivatives, gliomastins A-D (1-4), 9-O-methylgliomastin C (5), acremonin A 1-O-β-D-glucopyranoside (6), gliomastin E 1-O-β-D-glucopyranoside (7), and 6′-O-acetyl-isohomoarbutin (8), together with seven known analogues were isolated from the marine-derived fungus Gliomastix sp. Their structures were elucidated by extensive spectroscopic analysis including 1D and 2D NMR measurements aided by DFT NMR calculations as well as MS data. TDDFT-ECD and OR calculations were performed to determine the absolute configurations of 1 and the aglycones of 6 and 7. Compound 1 features a novel skeleton, biogenetically derived from a Diels-Alder reaction between derivatives of 11 and 13. Compound 2 represents a rare sulfur-containing alkaloid derived from the known hydroquinone 13. Compounds 1, 10 and 12 showed strong cytotoxicity against the L5178Y mouse lymphoma cell line with IC50 values of 1.8, 1.0 and 1.1 μM, respectively. Compound 3 exhibited moderate antitubercular activity against Mycobacterium tuberculosis with a MIC value of 12.5 μM.

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

Cc1cc(O)ccc1O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O

286.28 g/mol (C₁₃H₁₈O₇)