TY - JOUR
T1 - Non-geminal Aliphatic Dihalogenation Pattern in Dichlorinated Diaporthins from Hamigera fusca NRRL 35721
AU - Almeida, Celso
AU - Pérez-Victoria, Ignacio
AU - González-Menéndez, Víctor
AU - De Pedro, Nuria
AU - Martín, Jesús
AU - Crespo, Gloria
AU - Mackenzie, Thomas
AU - Cautain, Bastien
AU - Reyes, Fernando
AU - Vicente, Francisca
AU - Genilloud, Olga
PY - 2018/6/22
Y1 - 2018/6/22
N2 - Two new epimeric dihalogenated diaporthins, (9R∗)-8-methyl-9,11-dichlorodiaporthin (2) and (9S∗)-8-methyl-9,11-dichlorodiaporthin (3), have been isolated from the soil fungus Hamigera fusca NRRL 35721 alongside the known regioisomeric isocoumarin 8-methyl-11,11-dichlorodiaporthin (1). Their structures were elucidated by high-resolution mass spectrometry and NMR spectroscopy combined with molecular modeling. Compounds 1-3 are the first isocoumarins and the first halogenated metabolites ever reported from the Hamigera genus. The new compounds 2 and 3 display a non-geminal aliphatic dichlorination pattern unprecedented among known fungal dihalogenated aromatic polyketides. A bifunctional methyltransferase/aliphatic halogenase flavoenzyme is proposed to be involved in the biosynthesis of dichlorinated diaporthins 1-3. These metabolites are weakly cytotoxic.
AB - Two new epimeric dihalogenated diaporthins, (9R∗)-8-methyl-9,11-dichlorodiaporthin (2) and (9S∗)-8-methyl-9,11-dichlorodiaporthin (3), have been isolated from the soil fungus Hamigera fusca NRRL 35721 alongside the known regioisomeric isocoumarin 8-methyl-11,11-dichlorodiaporthin (1). Their structures were elucidated by high-resolution mass spectrometry and NMR spectroscopy combined with molecular modeling. Compounds 1-3 are the first isocoumarins and the first halogenated metabolites ever reported from the Hamigera genus. The new compounds 2 and 3 display a non-geminal aliphatic dichlorination pattern unprecedented among known fungal dihalogenated aromatic polyketides. A bifunctional methyltransferase/aliphatic halogenase flavoenzyme is proposed to be involved in the biosynthesis of dichlorinated diaporthins 1-3. These metabolites are weakly cytotoxic.
UR - http://www.scopus.com/inward/record.url?scp=85049031171&partnerID=8YFLogxK
U2 - 10.1021/acs.jnatprod.8b00041
DO - 10.1021/acs.jnatprod.8b00041
M3 - Article
AN - SCOPUS:85049031171
VL - 81
SP - 1488
EP - 1492
JO - Journal Of Natural Products
JF - Journal Of Natural Products
SN - 0163-3864
IS - 6
ER -