Pelageev DN et al. (2023), Dimeric (Poly)Hydroxynaphthazarins, Metabolites...

ECB-ART-51744

Mar Drugs 2023 Jul 19;217:. doi: 10.3390/md21070407.

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Dimeric (Poly)Hydroxynaphthazarins, Metabolites of Echinoderms and Lichens: The History of the Synthesis and Structure Elucidation.

Pelageev DN , Borisova KL , Anufriev VP .

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This review provides information on the synthesis and revision of the structures of natural dimeric (poly)hydroxynaphthazarins, metabolites of echinoderms and lichens, and on the refinement of the direction and mechanism of reactions in the synthesis of some of these compounds.

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References [+] :

Ageenko, Quinoid Pigments of Sea Urchins Scaphechinus mirabilis and Strongylocentrotus intermedius: Biological Activity and Potential Applications. 2022, Pubmed, Echinobase

	Figure 1. Ethylidene-bis(trihydroxynaphthazarin) 1, dibenzo[b,i]xanthentetraone 2 and two isomeric dibenzo[b,h]- (3) and dibenzo[c,h]- (4) xanthentetraones. In contrast to [20], all quinonoid compounds are depicted as derivatives of 1,4-naphthoquinone.
	Figure 2. Photography of sea urchins: (a) Spatangus purpureus; (b) S. droebachiensis; (c) Scaphechinus mirabilis.
	Scheme 1. Synthesis of biquinone 1 via aldol condensation of spinochrome D dimethyl ether 5 and acetaldehyde.
	Scheme 2. Cyclization of ethylidene-bis(trihydroxynaphthazarin) methyl ethers 6a–c to derivatives 7a–b, a key step in the synthesis of mirabiquinone (3).
	Scheme 3. Dimeric (poly)hydroxynaphthazarins 8–10, products of oxidative C-C or C-O coupling of ethylmompain (11a) and boryquinone (11b).
	Figure 3. Evolution of ideas about the structure of cuculoquinone.
	Figure 4. Starting substrates 14, 16 and key intermediates 15, 17 in the synthesis of isomeric bisnaphthazarins 13 and 8 [31].
	Figure 5. Photography of lichens and abyssal sea cucumbers in which cuculoquinone (8) was found: (a) Cetraria cucullata; (b) C. islandica; (c) Psychopotes longicauda; (d) a member of the genus Benthodytes.
	Figure 6. The structure of islandoquinone (18) as a result of a comparison of the compound with the structure of lapachol peroxide (19), and its correction in favor of gem-diol 20, considering the data of IR-spectroscopy.
	Figure 7. Four probable structures for islandoquinone.
	Figure 8. Starting substrates 22a,b for the synthesis of dioxabenzo[a]tetracenetetraones.
	Figure 9. (a) X-ray crystal structures of 23a,b. Crystal data: 23a triclinic, space group P-1, a 9.1095(4), b 9.9348(4), c 13.6026(5) Å, α 79.011(1), β 74.348(1), γ 85.296(1)°, V 1163.06(8) Å3, Z 2, Dc 1.725 g/cm3, F(000) 612, crystal size 0.40 × 0.35 × 0.20 mm. 23b triclinic, space group P-1, a 6.9265(2), b 10.5432(4), c 16.5567(6) Å, α 79.2460(10), β 81.6580(10), γ 80.2570(10)°, V 1162.65(7) Å3, Z 2, Dc 1.555 g/cm3, F(000) 568, crystal size 0.14 × 0.28 × 0.35 mm [45], (b) structural formulas of dioxabenzo[a]tetracenetetraones 23a,b,c.
	Figure 10. Photography of the lichen Lecanora hybocarpa.
	Figure 11. Hybocarpone (10) and related (5aS,6aS,12aS,12bS)-binaphtho[2,3-b; 2,3-d]furantetraones 24a,b [47].
	Scheme 4. Synthesis of hybocarpone (10) via SS-hexaketone intermediate 27.
	Figure 12. Key intermediates in hybocarpone synthesis described previously [47,49,50,51,52].
	Figure 13. The key intermediates 25b,c in the synthesis of binaphtho[2,3-b; 2,3-d]furantetraones 24a,b.
	Figure 14. The products of the oxidative coupling of hydroxynaphthazarin 31a (32a and 33a) and methylcristazarin (31b) (dimethyl ethers 32b and 33b).
	Figure 15. X-ray crystal structure of 33a. Crystal data: monoclinic, space group Pc, a 8.4327(3), b 21.6152(8), c 13.3512(5) Å, β 100.578(1)°, V 2392.23(15) Å3, Z 4, Dc 1.501 g/cm3, F(000) 1136, crystal size 0.20 × 0.25 × 0.35 mm [53].
	Scheme 5. SS- (34a) and RS- (35a) hexaketone intermediates, the precursors of the S,S,S,S- (32a) and S,R,R,S- (33a) binaphthofurantetraones.
	Figure 16. Calculated relative Gibbs energy of the possible dihydrobinaphthofurantetraones 32a, 32a′, 32a″ derived from the S,S-diastereoisomer 34a and 33a, 33a′, 33a″ derived from the R,S-diastereoisomer 35a [44,56]. (Values of the calculated energy of hybocarpone (10), its R,S-diastereoisomer 36 and other diastereomeric furan systems are presented in parentheses).
	Figure 17. R,S-Diastereoisomer of hybocarpone (10).
	Figure 18. Products of oxidative coupling reaction of dihydrolapachole 25c.
	Figure 19. The conversion of 39a–c→38→5 via retroaldol decomposition of keto form 40.
	Scheme 6. The conversion of 41→42→43 via heterodiene condensation of enone 44 and dienophile 45.
	Figure 20. The structures of benzo[g]chromedione 46 and echinochrom (47).
	Figure 21. Photography of producing mesocentroquinone sea urchins: (a) Mesocentrotus nudus; (b) Strongylocentrotus intermedius.
	Figure 22. Tautomerism of hydroxynaphthazarins.