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), C(14)H(19)BrO(2), 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), C(15)H(23)BrO(2), 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.
Laboratorio de Cristalografía y Química del Estado Sólido, DEQUIFIM, Facultad de Química, Universidad de la República, Av. Gral Flores 2124, Casilla de Correos 1157, Montevideo, Uruguay.
L
L
Suescun
A W
AW
Mombrú
R A
RA
Mariezcurrena
D
D
Davyt
R
R
Fernández
E
E
Manta
D000475:Alkenes / Q000737:chemistry*; D000818:Animals; D001048:Aplysia / Q000737:chemistry; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D000461:Rhodophyta / Q000737:chemistry*; D012717:Sesquiterpenes / Q000737:chemistry*; D013141:Spiro Compounds / Q000737:chemistry*
C428926:8-bromo-3,7,7-trimethyl-11-methylenespiro(5.5)-undec-1-ene-3,9-diol; C428925:8-bromo-9-hydroxy-7,7-dimethyl-11-methylenespiro(5.5)undec-1-en-3-one; D000475:Alkenes; D012717:Sesquiterpenes; D013141:Spiro Compounds