Unified synthesis and cytotoxic activity of 8-O-methylfusarubin and its analogues

Abstract

A unified total synthesis of 8-O-methylfusarubin, 8-O-methylanhydrofusarubin, fusarubin and anhydrofusarubin and their cytotoxic activities against six cancer cell lines are described.

Theoretical Investigation of Anhydrofusarubin: Structural and Optical Properties

“…For equatorial H28 atoms, the ν(CH) frequency in both calculations is predicted in the region of ν as (CH 3 ) vibrations of methyl groups. At the same time, for axial hydrogen atoms, the predicted ν(CH) frequency in both calculations is lower than the frequencies of ν s (CH 3 ) mode, possessing the frequency at 2927 cm −1 approximately [29,45]. This peak lies in the range typical for ν as (CH 2 ) modes [43].…”

“…With a larger peak width, it will be more similar to the contour of the bands from the spectrum of naphthazirin [46]. Only one peak has a frequency in the range of 1592-1603 cm −1 [22,26,29], which may be a consequence of the combination of several vibrational modes into one band. To illustrate this effect, Figure S3 shows the contours of the spectra in the range 400-1700 cm −1 obtained with different widths of individual lines.…”

“…Previous studies of anhydrofusarubin were carried out with its solution in chloroform and ethanol [22,24,28]. Only a few papers are devoted to anhydrofusarubin study in the crystalline state [20] with limited IR absorbance data [22,26,29]. In order to demonstrate more general spectroscopic peculiarities of a given compound regardless of the environment influence, below we consider vibrational spectra of the gas phase in a practically important range (375-4000 cm −1 ).…”

“…This pigment was extracted from Fusarium species and Chlamidosporum species fungi [19,26,27], and also was obtained by heating the pigment Fusarubin [28]. Moreover, the isolation of anhydrofusarubin from marine fungi B77 [20] and several ways of artificial synthesis of this compound have been investigated in a number of studies [16,29]. Despite the fact that this substance demonstrates antibiotic and antibacterial properties [20,24], recent interest has been devoted to its anhydrofusarubin cytotoxic activity against certain human cancer cells [27,29,30], in particular the acceleration of apoptosis of cancer cells at certain concentrations [27].…”

Six-membered ring systems: with O and/or S atoms

“…Several strategies have been developed to build O-6-membered heterocycles in the total synthesis of various natural compounds and their analogues, namely pyrans anhydrofusarubin and 8-O-methylanhydrofusarubin (19OBC7078), dihydropyrans actinorhodin (19AGE4264), (À)-secologanin, (À)-5-carboxystrictosidine and (À)-rubenine (19CEJ8996), fusarubin and 8-O-methylfusarubin (19OBC7078); tetrahydropyrans applanatumol B (19OL6199), aspergillide A (19JOC11848), (À)-englerin A and (À)-englerin B (19AGE8346) and putative structure of scholarein A (19OBC6831), chromenes cannabinol (19OL1212, 19OL6122), fontanesine B and its isomer (19HCA1900116), chromans-revised guignardones H and I (19OL3008), meroterpenoid azamerone (19JA2867), (À)-phomoarcherin C (19JOC14053), wikstrol A and wikstrol B (19OBC8206), isochromenes naphterpin, naphterpin B, naphterpin C, 7-demethylnaphterpin, debromomarinone, and isomarinone (19OL8312), 5,6-dihydropyran-2-ones cryptofolione and (þ)-strictifolione (19SC1031), putative structure of diplopyrone (19JOC666), (þ)-goniotriol (19TL151039), 5-hydroxy gonithalamin (19S780), parvistone C (19JHC815) and phosdiecin A (19JA13778), tetrahydropyran-2-ones (AE)-boschnialactone, (AE)-7-epi-boschnialactone, (AE)-teucrium lactone, (AE)-iridomyrmecin, (AE)-isoboonein, (AE)-7-epi-argyol, (AE)-scabrol A, (AE)-7-epi-scabrol A and (AE)-patriscabrol (19OBC6831), constanolactone A (19OBC4572), (þ)-goniopypyrone (19TL151039) and (AE)-pentalenolactone A (19JOC10172); coumarins dipetalolactone (19JHC99), goniothaline A and goniothaline B (19S552), lamellarin G trimethyl ether, lamellarin D trimethyl ether, lamellarin H, lamellarin h, dihydrolamellarin h, and lamellarin U (19JOC11596), myxocoumarin B (19OBC1966), palodesangren B trimethyl ether and palodesangren D dimethyl ether (19JOC13410), isocoumarins dehydroxanthomegnin and 9-O-methylpaepalantine (19EJO1145) and neonectrolides B, C, D and E (19JA15135), dihydroisocoumarins cladosporin (19TL831), (þ)-monocerin (19JOC6191) and dihydro eurotiumide B (19JOC16329), and finally, chromen-4-ones integrin and (AE)-oxyisocyclointegrin (19EJO1571).…”