First Syntheses of (-)-Tauranin and Antibiotic (-)-BE-40644 Based on Lipase-Catalyzed Optical Resolution of Albicanol

Abstract

First syntheses of sesquiterpene quinones (؊ ؊)-tauranin and (؊ ؊)-BE-40644 which exhibited strong cytotoxicity against several cancer cell lines, were achieved from (8aS)-albicanol obtained by enzymatic optical resolution. By comparison of the sign of specific rotation between synthetic (12bS)-BE-40644 and natural (؊ ؊)-BE-40644, the absolute configurations of natural (؊ ؊)-BE-40644 were determined to be 4aS, 6aS, 12aR, 12bS.

Purpurogemutantin and Purpurogemutantidin, New Drimenyl Cyclohexenone Derivatives Produced by a Mutant Obtained by Diethyl Sulfate Mutagenesis of a Marine-Derived Penicillium purpurogenum G59

“…The drimene skeleton occurs both in 5 S 9 S 10 S [12,13,14,17,18] and 5 R 9 R 10 R [10,11,19,20,21,22] forms in Nature. The combination of drimenyl (C-11) and cyclohexenone moiety (C-6′) affords four possible stereoisomers for 1 , as two pairs of enantiomers with absolute configurations, 5 S 9 S 10 S 4′ R 5′ R 6′ S ( A1 ) and 5 R 9 R 10 R 4′ S 5′ S 6′ R ( A2 ), 5 S 9 S 10 S 4′ S 5′ S 6′ R ( B1 ) and 5 R 9 R 10 R 4′ R 5′ R 6′ S ( B2 ), respectively.…”

“…A straightforward cyclization of the farnesyl group in I - 1 , followed by oxidation of gentisyl phenols and then epoxidation on the formed para -quinone ring, would give intermediates I - 2 , I - 3 , and 4 . The C-7′ carbaldehyde form of I - 2 [16], 5′-hydroxy I - 3 (tauranin) [12,13,17] and macrophorin A ( 4 ) [24] have been isolated from fungal metabolites. The hydration of I - 3 and hydrogenation of 4 would produce compounds 2 and 3 .…”

“…The same class of compounds having a regular drimane skeleton were also often isolated from both plant-associated [12,13,14,15] and marine-derived [16] fungi. Among them, (−)-taurinin [12,13,17], (−)-F-12509A [14,18], (+)-hyatellaquinone [11,19], (+)-zonarol [10,20,21] and (+)-zonarone [10,21,22] were synthesized [17,18,19,20,21,22] to determine their absolute configurations. Relative stereochemistry of the drimenyl unit in these compounds is the same as that in albicanol [23], a simple drimene alcohol with a hydroxymethyl group in the drimene skeleton.…”

Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol

“…Various methods to obtain enantioenriched (+)‐albicanol ( 1 ) are known that involve enzyme‐based kinetic resolution2a or separation of diastereomers. To the best of our knowledge, only two asymmetric syntheses of 1 are known in the literature.…”

Recent Advances in the Syntheses of Decalin Type Natural Products

“…The synthesis of (-)-99 and (-)-103 was shown in Scheme 13 35. Common aromatic building block, 4-[(t-butyldimethylsilyl)oxymethyl]-2,6-di(methoxymethyloxy)benzene for the syntheses of (-)-99 and (-)-103 was prepared from methyl 3,5-dihydroxybenzoate.…”