TY - JOUR
T1 - Isolation, ECD assisted structural analyses, biosynthetic discussions, and biological activities of epi-cochlioquinones D and its derivatives
AU - Arayama, Miki
AU - Nehira, Tatsuo
AU - Maeda, Hayato
AU - Tanaka, Kazuaki
AU - Miyagawa, Hisashi
AU - Ueno, Tamio
AU - Hosokawa, Seijiro
AU - Hashimoto, Masaru
N1 - Publisher Copyright:
© 2015 Elsevier Ltd.All rights reserved.
PY - 2015
Y1 - 2015
N2 - epi-Cochlioquinone D (1) and its 12-α-hydroxyderivative (2) were isolated from Helminthosporium velutinum TS28 based on antifungal screening against Cochliobolus miyabeanus. Relative configurations were established by the NMR analyses except for C5 locating far from the other asymmetric centers. ECD discussions involving spectral comparison with those of other related molecules as well as those based on theoretical calculations disclosed not only the C5 configuration but also the chirality for C12-C22 polycyclic moiety. H. velutinum TS28 also afforded precochlioquinol D (3), just the side chain component, which led us to discuss their biosynthetic pathway. Although 1 and 2 inhibit C. miyabeanus effectively, the C-14 epimeric cochlioquinones scarcely inhibited in spite of very close structures. Present study further revealed that C. miyabeanus tightly recognizes both the polycyclic moiety and the side chain. In contrast, both cochlioquinones and epi-cochlioquinones exhibited potent cytotoxicity against human colon adenocarcinoma (COLO 201) cells regardless of the C14 configuration as well as type of side chains.
AB - epi-Cochlioquinone D (1) and its 12-α-hydroxyderivative (2) were isolated from Helminthosporium velutinum TS28 based on antifungal screening against Cochliobolus miyabeanus. Relative configurations were established by the NMR analyses except for C5 locating far from the other asymmetric centers. ECD discussions involving spectral comparison with those of other related molecules as well as those based on theoretical calculations disclosed not only the C5 configuration but also the chirality for C12-C22 polycyclic moiety. H. velutinum TS28 also afforded precochlioquinol D (3), just the side chain component, which led us to discuss their biosynthetic pathway. Although 1 and 2 inhibit C. miyabeanus effectively, the C-14 epimeric cochlioquinones scarcely inhibited in spite of very close structures. Present study further revealed that C. miyabeanus tightly recognizes both the polycyclic moiety and the side chain. In contrast, both cochlioquinones and epi-cochlioquinones exhibited potent cytotoxicity against human colon adenocarcinoma (COLO 201) cells regardless of the C14 configuration as well as type of side chains.
KW - Absolute configuration
KW - Biological properties
KW - Biosynthetic discussions
KW - Calculations of ECD spectra
KW - Difference ECD spectra
KW - SAR study
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U2 - 10.1016/j.tet.2015.05.044
DO - 10.1016/j.tet.2015.05.044
M3 - Article
AN - SCOPUS:84949115632
SN - 0040-4020
VL - 71
SP - 4788
EP - 4794
JO - Tetrahedron
JF - Tetrahedron
IS - 29
ER -