Dendrodoa grossularia

The structure of the cytotoxic metabolite dendrodoine (81) from the tunicate Dendrodoa grossularia was determined by X-ray analysis [103] and it was later synthesised by a convergent route [104],... 

Novel indole derivatives continue to be found in marine organisms those reported recently include dendrodoine (3), a cytotoxic thiadiazole derivative, which occurs in the tunicate Dendrodoa grossularia, from Brittany,4 and the keto-lactam (4), one of two lactams isolated from the Caribbean sponge Hali-chondria melanodocia.5... 

Grossularins I (37) and II (38), the first examples of naturally occurring a-carbolines, were obtained from a French solitary tunicate (Dendrodoa grossularia) and were found to be cytotoxic toward L1210 leukemia cells (55). Previously the structure of grossularin I was proposed as 39 (56), which was revised to 37 on the basis of comparison with the structure of grossularin II (38). Structural proof for 38 was unambiguously provided by X-ray analysis. The same tunicate contained 3-indolyl-4//-imidazol-4-one (40), the structure of which was confirmed by synthesis (57). The imidazo-lone compound (40) was devoid of cytotoxicity. 

Grossularine-1 (1) is a natural product isolated from the tunicate Dendrodoa grossularia (Stylidae) and possesses interesting antitumor properties. In a recent approach the tetracyclic ester 2 as key intermediate for the synthesis of 1 was constructed from the heterocycles X and Y performing the following transformations ... 

Dendrodoine (109) [80,81], the related aminoimidazole (110) analogue [82] and the recently reported oxadiazinone, alboinon (111) [83] were reported from Dendrodoa grossularia. There are structural similarities between these tryptophane-derived metabolites, the phenylalanine-derived metabolites (5), (6) and (7), and the tyrosine-derived metabolite... 

When the approach in Scheme 67 was attempted for the synthesis of alboinon 381 (a natural product from marine organism Dendrodoa grossularia), it was discovered that the oxadiazine system does not survive even the mildest of the SEM deprotection conditions. Therefore, an alternative method, starting from imidazole, via a Baeyer-Villiger approach was improvised <1997T2055> (see Section 9.09.9.4). 

Dendrodoa grossularia was the source of several indole alkaloids with different heterocyclic moieties linked at the 3-position (compounds 210-213) [154, 108-210]. 

Guyot, M., Meyer, M., (1986). An 3-indolyl-4H-imidazol-4-one from the tunicate Dendrodoa grossularia. Tetrahedron Lett. 21,262 -2622. 

Bergmann, T., Schories, D., Steffan, B., (1997). Alboinon, an oxadiazinone alkaloid from the ascidian Dendrodoa grossularia. Tetrahedron 53,2055-2060. 

The First S -N Bond in a Natural Product —Dendrodoine, of which 98 mg was isolated from 2.2 tonnes of a marine tunicate, Dendrodoa grossularia (Styelidae), has been shown by JT-ray and spectral data to be an indole derivative of 1,2,4-thiadiazole (139). A noteworthy feature is that, as far as this Reporter is aware, this is the first natural product with a sulphur(ii)-nitrogen bond. All the other fourteen possible combinations of the five common biological elements (C, H, N, O, and bivalent S) are elaborated by living cells only S—N has, so far, been missing. 

S. Heitz, M. Durgeat, M. Guyot, C. Brassy, B. Bachet, Nouveau derive indohque du thiadiazole-1,2,4, isole d un tunicier Dendrodoa grossularia), Tetrahedron Lett. 21 (1980) 1457-1458. 

Moquin, C., and M. Guyot Grossularine, a Novel Indole Derivative from the Marine Tunicate, Dendrodoa grossularia. Tetrahedron Lett. 25, 5047 (1984). 

Mainly, the common Dendrodoa grossularia (baked bean ascidian, gooseberry seasquirt). Most of alkaloids isolated from spedes of the genus Dendrodoa contain a guanidine residue, often assodated to the a-carboline system. 

Jimenez, C., Quinoa, E., Castedo, L., and Riguera, R. (1986) Epidioxysterols from the tunicates Dendrodoa grossularia and AscidieUa aspersa, and the gastropoda Aplysia depdans and Aplysia punctata. J. Nat. Prod., 49, 905—909. 

Loukaci, A., Guyot, M., Chiaroni, A., and Riche, C. (1998) A new indole alkaloid from the marine tunicate Dendrodoa grossularia. ]. Nat. Prod., 61, 519-522. 

Moquin, C. and Guyot, M. (1984) Grossularine, a novel indole derivative from the marine tunicate, Dendrodoa grossularia. Tetrahedron Lett., 25, 5047-5048. 

Hogan, I.T. and Sainsbury, M. (1984) The synthesis of dendrodoine a metabolite of the tunicate Dendrodoa grossularia (S-3-(N,N-dimethylamino-l,2,4-thiadiaxolyl)-3-indolylmethanone. Tetrahedron, 40, 681-682. 

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