Retipolides - unusual spiromacrolactones from the mushrooms Retiboletus retipes and R. ornatipes
Publikation: Beiträge in Zeitschriften › Zeitschriftenaufsätze › Forschung
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Retipolides - unusual spiromacrolactones from the mushrooms Retiboletus retipes and R. ornatipes. / Justus, Karl; Herrmann, Rupert; Klamann, Jörg-Dieter et al.
in: European Journal of Organic Chemistry, Jahrgang 2007, Nr. 33, 01.11.2007, S. 5560-5572.Publikation: Beiträge in Zeitschriften › Zeitschriftenaufsätze › Forschung
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TY - JOUR
T1 - Retipolides - unusual spiromacrolactones from the mushrooms Retiboletus retipes and R. ornatipes
AU - Justus, Karl
AU - Herrmann, Rupert
AU - Klamann, Jörg-Dieter
AU - Gruber, Gertraud
AU - Hellwig, Veronika
AU - Ingerl, Andrea
AU - Polborn, Kurt
AU - Steffan, Bert
AU - Steglich, Wolfgang
PY - 2007/11/1
Y1 - 2007/11/1
N2 - Mushrooms of the genus Retiboletus contain the retipolides A-D (1, 6-8), unusual 14-membered spiromacrolides with a biphenyl ether linkage. The structures of these metabolites suggested a biogenetic sequence starting from retipolide E (16), which could furnish the unique 2(3H)-oxepinone unit of retipolide C (7) via an oxidative enlargement of the 4-hydroxyphenyl ring. A subsequent O/C-acyl shift would then lead to the cyclopenta[c]pyran system of retipolide A (1). The proposed precursor 16 was synthesized and subsequently detected in the fungal extract in addition to the probable biosynthetic intermediates butyrolactone II (13), tyrosol (14), and secoretipolide E (15). The structural elucidation of retipolide A (1) was accomplished after transformation into a methoxyfulvene derivative 2a, and the absolute (R) configuration of 1 was assigned by a single-crystal X-ray analysis of the corresponding (S)-sec-butoxyfulvene analogue 2b. Some samples of R. retipes/ornatipes contained isoretipolide A (9), an isomer of 1 with a highly strained 12-membered lactone ring incorporating two C,C-coupled 4-hydroxyphenyl units. A comparison of the CD spectrum of retipolide A (1) with those of the other retipolides and isoretipolide A (9) indicates that all of these macrolides possess R configuration.
AB - Mushrooms of the genus Retiboletus contain the retipolides A-D (1, 6-8), unusual 14-membered spiromacrolides with a biphenyl ether linkage. The structures of these metabolites suggested a biogenetic sequence starting from retipolide E (16), which could furnish the unique 2(3H)-oxepinone unit of retipolide C (7) via an oxidative enlargement of the 4-hydroxyphenyl ring. A subsequent O/C-acyl shift would then lead to the cyclopenta[c]pyran system of retipolide A (1). The proposed precursor 16 was synthesized and subsequently detected in the fungal extract in addition to the probable biosynthetic intermediates butyrolactone II (13), tyrosol (14), and secoretipolide E (15). The structural elucidation of retipolide A (1) was accomplished after transformation into a methoxyfulvene derivative 2a, and the absolute (R) configuration of 1 was assigned by a single-crystal X-ray analysis of the corresponding (S)-sec-butoxyfulvene analogue 2b. Some samples of R. retipes/ornatipes contained isoretipolide A (9), an isomer of 1 with a highly strained 12-membered lactone ring incorporating two C,C-coupled 4-hydroxyphenyl units. A comparison of the CD spectrum of retipolide A (1) with those of the other retipolides and isoretipolide A (9) indicates that all of these macrolides possess R configuration.
KW - Chemistry
KW - Basidiomycetes
KW - Macrolactones
KW - Natural products
KW - Oxepinones
KW - Retipolides
KW - Spiro compounds
UR - http://www.scopus.com/inward/record.url?scp=36348950256&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/b123d300-9560-3841-aa23-32427ef229fc/
U2 - 10.1002/ejoc.200700579
DO - 10.1002/ejoc.200700579
M3 - Journal articles
VL - 2007
SP - 5560
EP - 5572
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 33
ER -