Mytilus edulis Azaspiracid

Satake M, Ofuji K, Naoki H, James KJ, Furey A, Mcmahon T, Silke J, Yasumoto T (1998) Azaspiracid, a new marine toxin having unique spiro ring assemblies, isolated from Irish mussels, Mytilus edulis. J Am Chem Soc 120 9967-9968 Scheuer PJ, Takahashi W, Tsutsumi J, Yoshida T (1967) Ciguatoxin isolation and chemical nature. Science 155 1267-1268... 

Ofuji, K., et al.. Two analogs of azaspiracid isolated from mussels, Mytilus edulis, involved in human intoxication in Ireland, Nat. Toxins, 7, 3, 99, 1999. 

In 1995, a report of human illness with diarrhetic shellfish poisoning (DSP)-like symptoms in the Netherlands was eventually found to result from the consumption of poisoned mussels (Mytilus edulis) harvested from Killary Harbour, Ireland (McMahon 1996). Yasumoto, Satake, and co-workers eventually isolated and proposed a stracture for the causative agent of this condition azaspiracid-1 (la. Fig. 16.1). The unique polyether stracture of azaspiracid-1 (la) is characterized by several spiro-cyclic systems, including an azaspiro ring fused to a 2,9-dioxabicyclo[3.3.1]nonane system and a terminal carboxylic acid. In total, there are nine rings and twenty stereogenic centers within the structure proposed by Yasumoto and co-workers in 1998 (Satake 1998). This stracture was based primarily on NMR spectroscopic data and did not include absolute stereochemistry, nor did it specify relative stereochemistry between the ABCDE and FGHI domains. 

The isolation of azaspiracid-1 from poisonous mussels (Mytilus edulis) by Yasumoto and Satake was an admirable and Herculian accomplishment. Its originally proposed structure by these investigators stimulated considerable efforts to synthesize it in the laboratoiy. The efforts in om laboratory led first to the demise of the originally proposed structures and subsequently to the proposal and total synthesis of the correct structure of this fascinating natural product. 

Hess, E, Nguyen, L., Aasen, I, Keogh, M., Kilcoyne, J, McCarron, P., and Aune, T. 2005. Tissue distribution, elFects of cooking and parameters affecting the extraction of azaspiracids from mussels, Mytilus edulis, prior to analysis by liquid chromatography coupled to mass spectrometry. Toxicon 46, 62—71. 

Satake, M., Ofuji, K., Naoki, H., James, K., Furey, A., McMahon, T, Silke, X, and Yasumoto, T. 1998a. Azaspiracid, a New Marine Toxin Having Unique Spiro Ring Assemblies, Isolated from Irish Mussels, Mytilus edulis. JAm Chem Soc 120,... 

Azaspiracid poisoning (AZP) is the most recently discovered of the toxic syndromes from shellfish consumption. The symptoms of acute AZP intoxication closely resembles those associated with diarrhetic shellfish poisoning (DSP), and include diarrhea, vomiting, and headache and the first confirmed incident was in 1995 (Netherlands), following the consumption of mussels (Mytilus edulis) that were cultivated in Ireland (Satake et al., 1998). Since these symptoms are similar to bacterial enterotoxin poisoning, and analytical methods for the detection of these toxins have only been developed in recent years, it is probable that there have been many unreported cases of this poisoning. The first azaspiracid to be identified was AZAl (Figure 35.1, = H R = CH3),... 

In the present experiments, azaspiracid-1 (AZA) was used for pathological studies. AZA was extracted from blue mussels, Mytilus edulis, collected in Ireland in 1996 and 1997 (Satake... 

R = R = Me, Scheme 15.27), was reported by Yasumoto et al. as an isolated compound from the cultivated Irish mussel Mytilus edulis. The azaspiracid natural products display... 

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