Two Natural Products from the Algae Laurencia scoparia

The structures and absolute stereochemistries of two chamigrene-type metabolites (spiro­[5.5]­un­decane derivatives) isolated from the red algae Laurencia scoparia are described. One, a non-sesquiterpene named maĩlione (8-bromo-9-hydroxy-7,7-di­methyl-11-methyl­ene­spiro­[5.5]­undec-1-en-3-one), C14H19BrO2, was detected previously in Laurencia cartilaginea, while the other, the sesquiterpene isorigidol (8-bromo-3,7,7-tri­methyl-11-methyl­ene­spiro­[5.5]-undec-1-ene-3,9-diol), C15H23BrO2, is a new isomer of rigidol, first isolated from Laurencia rigida. The A rings of these spiro­cyclic compounds show the same carbon skeleton. However, the relative stereochemistry of the 8-Br and 9-OH substituents is different. While maĩlione displays the usual syn (or cis) relative stereochemistry of the bromo­hydroxy vicinal group, isorigidol shows an anti (or trans) arrangement. The 8-Br and 9-OH groups are both in equatorial positions in isorigidol, while the 9-OH group is axial in maĩlione, as in most chamigrenes. The absolute configurations of the chiral centers were determined as 6S, 8S and 9R in maĩlione, and 3R, 6S, 8S and 9S in isorigidol.