Dinogunellins A-D, ichthyootoxic phospholipids, have been isolated from the mature eggs of the northern blenny Stichaeus grigorjewi. Their structures were determined based on spectral and chemical methods as a mixture of 2'-or 3'-acylated adenosine 5'-phosphate linked to the α-carboxyl group of L-asparagine through a P-N bond. and named dinogunellins A-D (2-5). Surprisingly, their structures differed from that proposed in the earlier work. This paper describes the isolation and structure determination of these four new compounds.
RESULTS AND DISCUSSIONThe frozen eggs (300 g, wet weight) of S. grigorjewi were homogenized and extracted with CHCl 3 /MeOH (2:1). The CHCl 3 layer obtained after solvent partitioning was purified by silica gel column chromatography and reverse-phase high-performance liquid chromatography (HPLC) to obtain dinogunellins A-D. However, the isolated dinogunellin A (2) gave two peaks corresponding to dinogunellins A and B when analyzed by HPLC, whereas dinogunellin B (3) also gave two peaks corresponding to dinogunellins A and B (Fig. 1). Dinogunellins C and D showed the similar feature. Therefore, it was concluded that dinogunellins A and B as well as dinogunellins C and D were interconvertible to each other. The mixture of dinogunellins A and B was further purified by HPLC using a gel-filtration column to afford a mixture of dinogunellins A and B (41.3 mg, 13.8 × 10 -3 % yield based on wet wt), while 3.3 mg of the mixture of dinogunellins C and D (1.1 × 10 -3 %) was similarly prepared.