Three previously unknown diterpenes -spirosphaerol (1), anthrasphaerol (2) and corfusphaeroxide (3) -have been isolated from the red alga Sphaerococcus coronopifolius. Their structures were elucidated by spectral analysis, including
[a]General: Optical rotations were measured with a Perkin-Elmer model 341 polarimeter and a 10 cm cell. UV spectra were recorded with a Shimadzu UV-160A spectrophotometer. IR spectra were obtained with a Bruker Tensor 27 spectrometer. NMR spectra were recorded with Bruker AC 200 and Bruker DRX 400 spectrometers. Chemical shifts are given on a δ scale (ppm) with reference to the solvent signals. The 2D experiments (HSQC, HMBC, COSY, NOESY) were performed with use of standard Bruker pulse sequences. High-resolution ESI mass spectra were measured in positive mode with a Thermo Scientific LTQ Orbitrap Velos mass spectrometer (Institute of Biology, Medicinal Chemistry and Biotechnology, National Hellenic Research Foundation). Low-resolution EI and CI mass spectra were measured with a Thermo Electron Corporation DSQ mass spectrometer and a Direct-Exposure Probe, with CH 4 as reagent gas. Vacuum liquid chromatography was performed with Kieselgel 60 (Merck), and gravity column chromatography was performed with Kieselgel 60H (Merck). Thinlayer chromatography (TLC) was performed with Kieselgel 60 F 254 aluminium support plates (Merck), and spots were visualized after spraying with H 2 SO 4 in MeOH (15 %, v/v) reagent followed by heating. HPLC separations were conducted with an Agilent 1100 model equipped with refractive index detector and a Kromasil 100 C18 5µ (250 ϫ 8 mm) HPLC reversed-phase column or a Supelco-Sil 5µ (250 ϫ 10 mm) HPLC normal-phase column. The structures in Figures 1, 2, and 3 were generated and optimised (energy: 37.26, 33.73 and 43.30 kcal mol -1 , respectively) by use of "HyperChem™ Professional 8.0.8" molecular modelling and simulation software (force field: MM+; optimisation algorithm: Polak-Ribiere). Plant Material: S. coronopifolius was collected by SCUBA diving in Liapades Bay, Corfu, Greece, at a depth of 8-15 m in June 2009. A voucher specimen is kept at the Herbarium of the Laboratory of Pharmacognosy and Chemistry of Natural Products, University of Athens (ATPH/MP0140).Extraction and Isolation: S. coronopifolius was initially freeze-dried (149.2 g dry weight) and then exhaustively extracted with CH 2 Cl 2 / MeOH mixtures (3:1) at room temperature. The combined extracts were concentrated to give a dark green residue (4.2 g), which was later subjected to vacuum liquid chromatography on silica gel, with use of a 2 % step gradient of cyclohexane/EtOAc elution sequence. Fraction F4 (4 % EtOAc in cyclohexane, 2.35 g) was fractionated by gravity column chromatography, with use of a 1 % step gradient of cyclohexane/EtOAc. Fraction F4.3 (8 % EtOAc in cyclohexane, 1.02 g) was further separated by reversed-phase HPLC, with use of www.eurjoc.org 2852 CH 3 CN as the mobile phase. Peak F4.3.9 (t R 11.4 min, 11.7 mg) was further purified by normal-phase HPLC, with use of 15 % Et...