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J. Braz. Chem. Soc. vol.9 número2

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Academic year: 2018

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In Bra zil, the re has been a slow but con ti nu ous in cre a se in the in te rest for ma ri ne na tu ral pro ducts re se arch along the past 20 ye ars. In the first part of this re vi ew, stu di es re la ted to iso la ti on and struc tu re de ter mi na ti on were des cri -bed9. The se cond part of this re vi ew is de di ca ted to synthe -sis. The ma jor pu blis hed re sults of works done in Bra zil will now be dis cus sed in the fol lo wing sec ti ons. The con tent of me e ting abs tracts, usu ally inac ces si ble to most fo re -ign sci en tists, is in clu ded.

Synthe sis of Ma ri ne Na tu ral Pro ducts

The first Bra zi li an con tri bu ti ons in the fi eld of or ga nic synthe sis were made by Rú ve da and co-workers who synthe si zed some di ter pe nes from spon ges and sea ha res di ter pe nes, or the ir enan ti o mers, from the re a dily ava i la ble co pa lic acid (2). Se ve ral ses qui ter pe nes were also the ob -ject of to tal synthe ses. More re cently, pre li mi nary stu di es

have ap pe a red on the synthe ses of one ses ter ter pe ne, one ma cro li de and ni tro gen-containing me ta bo li tes.

Di ter pe nes

The first tar get was the tricy clic di ter pe ne iso apl ysin-20

(3), that had been iso la ted from the sea hare Aplysia ku ro dai, col lec ted in Ja pan, and for which the ste re o che mistry at C-13 had re ma i ned un cle ar10. The de bro mo ho mo lo gue 4

was synthe si zed from co pa lic acid (2), fol lo wing Sche me 1, in an eight-step se quen ce with an ex cel lent ove rall yi eld (49%)11. Thus, methyl iso co pa la te 6 was pre pa red by es te ri -fi ca ti on of 2 into 5 and acid-catalyzed for ma ti on of the C-ring. Oxi da ti on of the tri subs ti tu ted dou ble bond with OsO4 fur nis hed the ex pec ted β-ori en ted αglycol. The oxy -gen func ti on at C-12 was then eli mi na ted in the usu al way, by oxi da ti on to ke to ne 8, thi o ke tal for ma ti on and hydro ge -noly sis on Ra ney-Ni into 10, which was fi nally re du ced to de bro mo-isoaplysin-20 (4)11.This work fi xed the re la

-Sche me 1. Synthe sis of the sup po sed struc tu re of de bro mo i so apl ysin-20.

a. CH2N2, Et2O; b. HCOOH 98% aq; c. OsO4, dry Py , r.t., 65 h; d. Na2S2O5 , Py/H2O, 2,5 h ; e. DMSO / Ac2O, r.t., 27h ; f. HSCH2CH2SH /

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