Total Synthesis of the Cytotoxic Marine Triterpenoid Isodehydrothyrsiferol Reveals Partial Enantiodivergency in the Thyrsiferol Family of Natural Products.
Recently, the phenomenon of enantiodivergence was uncovered as a new phenomenon in the biosynthesis of natural products. In nature, chiral natural products are usually produced in optically active form, but both enantiomers sometimes arise in different genera and/or species or in a single species. Here we show through enantioselective total synthesis that the natural product isodehydrothyrsiferol shows partial enantiodivergency in that six of the nine or ten asymmetric centers are enantiomeric to those of other members of the marine squalene-derived triterpenoid thyrsiferol family. In addition, isodehydrothyrsiferol and dehydrothyrsiferol, which show partial enantiodivergency, were isolated from the same producer, the red alga Laurencia viridis. These results demonstrate that partial enantiodivergence can develop even between natural products originating from a single species.
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Akihiro
A
Hoshino
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Haruka
H
Nakai
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Miyako
M
Morino
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Keisuke
K
Nishikawa
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Takeshi
T
Kodama
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Kento
K
Nishikibe
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Yoshiki
Y
Morimoto
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D044722:Laurencia / Q000737:chemistry*; D008968:Molecular Conformation; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D013237:Stereoisomerism
D001688:Biological Products; D005663:Furans; D011714:Pyrans; C410452:thyrsiferol
biosynthesis; configuration determination; cytotoxicity; natural products; total synthesis