Structure of antibiotic X-14547A, a carboxylic acid ionophore produced by Streptomyces antibioticus, NRRL 8167

Journal of the American Chemical Society
1978.0

Abstract

Three studies are reported: 1) (CH3CAs)Co2(CO)6 (Va) and (PhCAs)Co2(CO)6 (Vb) were synthesized by reacting 1,1-dichloroethyldichloroarsine or α,α-dichlorobenzyllithium with dicobalt octacarbonyl, yielding 27% and 28% respectively. They were characterized by MS, NMR, IR and showed reactions with triphenylphosphine, acetylation (Vb), but not alkylation. Thermal decomposition of Vb produced Co2As, and oxidation cleaved C-As bonds. The synthesis can be extended to other type IV clusters. 2) Antibiotic X-14547A, a second nitrogen-containing carboxylic acid ionophore, was isolated from Streptomyces antibioticus. Its structure was determined by X-ray analysis of its (R)-(+)-1-amino-1-(4-bromophenyl)ethane salt (2:1 stoichiometry), revealing a novel 1(E),3(E)-butadiene system and trans fused tetrahydroindan, and it transports Ca2+. 3) Acid-catalyzed rearrangement of bicyclomycin gave diastereomers 2a,b. Converting to p-bromobenzoates allowed separation, and X-ray analysis of the trans isomer (3) established bicyclomycin's absolute configuration as 1S,6R,1'S,2'. Racemic 2a,b was synthesized via condensation of N,N-diacetylglycine anhydride with aldehyde 6.

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