Absolute stereochemistry of antifouling cembranoid epimers at C-8 from the Caribbean octocoral Pseudoplexaura flagellosa. Revised structures of plexaurolones

• Published in: Tetrahedron Vol. 67; no. 47; pp. 9112 - 9121
• Main Authors: Tello, Edisson, Castellanos, Leonardo, Arevalo-Ferro, Catalina, Rodríguez, Jaime, Jiménez, Carlos, Duque, Carmenza
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 25.11.2011; Elsevier
• Subjects: Alicyclic compounds, terpenoids, prostaglandins, steroids; Antifouling; Bacteria; Bacterial biofilm inhibition; Biofilms; Cembranes; Central America/Caribbean; Chemistry; Chemistry, Organic; Exact sciences and technology; Inhibition; Inhibitors; Organic chemistry; Physical Sciences; Plexaurolones; Preparations and properties; Pseudomonas aeruginosa; Pseudoplexaura flagellosa; Quorum sensing inhibition; Science & Technology; Stereochemistry; Terpenoids; Pseudoplexaura flagellosa; Cembranes; Plexaurolones; Bacterial biofilm inhibition; Quorum sensing inhibition; Antifouling; CONFIGURATION; ASSIGNMENT; ACETATE; Terpenoid; Molecular structure; Epimer; Animal origin; Marine environment; Coelenterata; Terpene; Antifouling protection; Cnidaria; Absolute configuration; Biofilm; Diterpene; Quorum sensing; Inhibition; Invertebrata
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.09.094

Eight cembranoid epimers at C-8 ( 1– 8) were isolated from the organic extract of the Colombian Caribbean octocoral Pseudoplexaura flagellosa. Compounds 2, 4, and 6 are reported for the first time. Although compounds 1, 3, 5, 7, and 8 have been reported previously, their structures and NMR assignments are revised, completed or corrected. The structures of these compounds were established on the basis of detailed analysis of their spectroscopic data. Furthermore, the relative configurations of compounds 1– 3 and 7 were confirmed by single-crystal X-ray diffraction. The absolute configurations of compounds 1– 8 were determined using a combination of the modified Mosher method and unambiguous chemical interconversions. Evaluation of their antifouling properties using quorum sensing inhibition (QSI) and biofilm inhibition bioassays showed that compounds 3, 6, and 7 have excellent QSI activity against Chromobacterium violaceum, as measured by inhibition of the production of violacein pigment, without interfering with its growth. Furthermore, compounds 3, 5, 6, and 8 exhibited inhibition of biofilm maturation without interfering in the growth of Pseudomonas aeruginosa, Vibrio harveyi, and Staphylococcus aureus. This is the first report of cembranoids as inhibitors of bacterial biofilm and as compounds that interfere with QS in C. violaceum. [Display omitted]