Cyclodepsipeptides

In contrast, jasplakinolide, a cyclodepsipeptide from the marine sponge Jaspis johnstoni, rapidly penetrates the cell membrane. It competes with phalloidin for F-actin binding and has a dissociation constant of approximately 15 nM. It induces actin polymerization and stabilizes pre-existing actin filaments. Dolastatin 11, a depsipeptide from the mollusk Dolabella auricu-laria, induces F-actin polymerization. Its binding site differs from that of phalloidin or jasplakinolide. 

Figure 31 Adamantane-bridged tyrosine-based cyclodepsipeptides are suitable models for host-guest studies and they are also able to act as ion transporters. Taken from Ref. [161] with permission.

Initially PDPs were synthesized by stepwise polycondensation of linear activated depsipeptide [93]. In 1985, Helder, Feijen and coworkers reported the synthesis of PDPs by ROP of a morpholine-2,5-dione derivative (cyclic dimer of ot-hydroxy- and a-amino acid cyclodepsipeptide, cDP) [94, 95]. The ROP method gives an alternative type of PDP by homopolymerization and also allows the copolymerization with other monomers (lactones and cyclic diesters) including LA, GA, and CL to give a wide variety of functional biodegradable materials. The synthesis of PDPs as functional biomaterials has been recently reviewed [17]. 

Complete structural analysis requires mass spectral and NMR data as well as chemical degradation and analysis of the chirality of the constituent amino acids, determination of the mode of linkage of lysine (a- or s-), the size of the cyclopeptide or cyclodepsipeptide ring, etc. (37). In some cases sttuctures have been proposed based only on mass spectral data. Difficulties arising in this approach were discussed (44). To determine the three-dimensional structure an X-ray... 

Alterobactin A is a cyclodepsipeptide from Alteromonas luteoviolacea, with A -DHB-(4S),8-diamino-(3/ )-hydroxy-octanolyl-D-Ser-Gly-L-Arg-L-f/ireo-3-hydroxy-Asp-Gly-L-f/treo-3-hydroxy-Asp having an ester bond between the C-terminal carboxyl group and Ser. It is accompanied by its hydrolysis product alterobactin B (Fig. 8, 26, 27) (298). Alterobactin A forms a 1 1 complex with Fe " with an... 

Pyoverdins with a C-terminal 1 (Lys-FoOFIOm-Ser) cyclodepsipeptide or a free carboxyl group ... 

Scheme 18 shows a remarkable approach towards cyclodepsipeptides that includes Zhu-3CR as the key step of a tandem deprotection/cyclization strategy... 

Scheme 18 Synthesis of cyclodepsipeptides by a domino MCR/deprotection/activation/cycliza-tion strategy...

A rapid synthesis of cyclodepsipeptides containing sugar moieties was reported by Zhu and coworkers (Scheme 20) [88]. A three-component reaction of a sugar amino acid derivative 20a, an aldehyde b, and a dipeptide isocyanide c, followed by saponification and trifluoroacetic acid-promoted macrocyclization was employed to afford the cyclic amino sugar cyclopeptides d. This approach allows to systematically modify the amino acids and the carbohydrate residue, as well as the size of the macrocycle. Again, the only reagents used to mediate the formation of the... 

Scheme 20 Cyclodepsipeptides containing sugar amino acids...

The monamycins are a group of 15 antibiotic cyclodepsipeptides from Strepto-myces jamaicensis. After much structural elucidation work on the hydrolysis and degradation products (1050, 1051), the structures of the six chlorine-containing monamycins Gi (1015), G2 (1016), G3 (1017), H, (1018), H2 (1019), and I (1020) were determined (1052). 

Bevan K, Davies JS, Hassall CH, Morton RB, Phillips DAS (1971) Amino-Acids and Peptides. Part X. Characterisation of the Monamycins, Members of a New Family of Cyclodepsipeptide Antibiotics. J Chem Soc (C) 514... 

Synthesis, Conformational Analysis, and Cytotoxicity of New Analogues of the Natural Cyclodepsipeptide Jaspamide. J Nat Prod 67 1325... 

Synthesis, Solution Structure, and Bioactivity of Six New Simplified Analogues of the Natural Cyclodepsipeptide Jaspamide. Bioorg Med Chem 13 5225... 

Tinto WF, Lough AJ, McLean S, Reynolds WF, Yu M, Chan WR (1998) Geodiamolides H and I, Further Cyclodepsipeptides from the Marine Sponge Geodia sp. Tetrahedron 54 4451... 

D Auria MV, Paloma LG, Minale L, Zampella A, Debitus C, Perez J (1995) Neosiphonia-molide A, a Novel Cyclodepsipeptide, with Antifungal Activity from the Marine Sponge Neosiphonia superstes. J Nat Prod 58 121... 

Clark DP, Carroll J, Naylor S, Crews P (1998) An Antifungal Cyclodepsipeptide, Cyclolithistide A, from the Sponge Theonella swinhoei. J Org Chem 63 8757... 

Bachmann and Seebach [159] have reported the preparation and characterization of cyclic lactones (MeCHCH2C(0)0)n, where n = 4 and 8. The reaction product between butyl lithium in benzene and the solid polystyrene support PS-C6H4CH2NH2 leads to a lithiated species that can be represented as PS-Cfd bCI 12N11 Li(BuI i)x, where x 4 is active in the ring-opening of the cyclic esters L-lactide, rac-lactide, and 2,5-morpholinediones, leading to their respective cyclic oligoesters and cyclodepsipeptides (Fig. 49) [160]. The... 

K Mochizuki, K Oomori, H Tamura, Y Shizuri, S Nishiyama, E Miyoshi, S Yama-mura. The structures of bioactive cyclodepsipeptides, beauveriolide I and II, metabolites of entomopathogenic fungi Beauveria sp. Bull Chem Soc Jpn 66 3041-3046, 1992. 

H Tomoda, XH Huang, J Cao, H Nishida, R Nagoa, S Okuda, H Tanaka, S Omura. Inhibition of acyl-CoA cholesterol acyltransferase activity by cyclodepsipeptide antibiotics. J Antibiot 45 1626-1632, 1992. 

T Sasaki, M Takagi, T Yaguchi, S Miyadoh, T Okada, M Koyama. A new anthelmintic cyclodepsipeptide PF1022. J Antibiot 45 692-697, 1992. 

A Suzuki, M Kanaoka, A Isogai, S Murakoshi, M Ichinoe, S Tamura. Bassianolide, a new insecticidal cyclodepsipeptide from Beauveria bassiana and Verticillium lecanii. Tetrahedron Lett 25 2167-2170, 1977. 

P Jeschke, G Bonse, G Thielking, W Etzel, A Harder, N Mencke, H Kleinkauf, R Zocher, K Iinuma, K Miyamoto. Process for the preparation of substituted aryl lactic acid containing cyclodepsipeptides with 24 ring atoms. WO9720945 (Bayer AG), 1998. 

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