Synthesis of erivanin and 1-epierivanin from 1-(α)-santonin

Harapanhalli, Ravi S.

doi:10.1039/p19880002633

Cited by 15 publications

(4 citation statements)

References 5 publications

(8 reference statements)

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“…3 Hz, H-3a), 2.39 (1H, ddq J4a,l; = 7. 5 Hz,7^=7^= 5. 3 Hz, H-4a),2.33(lH,dqJ117=12.2HzJ1113=6.9Hz,H-l^), 1.19(3H,dJ1311=6.9Hz,Me-13), 1.0K3H, s, Me-14), 0.96 (3H, d j154 = 7.5 Hz, Me-15); 13C nmr (CDC13) 40.2 (C-l), 25.9 (C-2), 73.0 (C-3), 34.4 (C-4), 49.7 (C-5), 80.1 (C-6), 53.6 (C-7), 23.5 3a-Hydroxy-4a,5a, 11 ß--eudesman-óa, 12-olide [3]•-Mp 116-118°, [a]25D -54°(c= 1, CHC13); ir vmax(CHCl3) 3460,1767 cm™1;'Hnmr(CDCl3)6 3.93(1H,ddj65 = l 1.6 ,767 = 10.0 , -6ß), 3.85 (lH,dddJ34a=/32a=-/329 = 2.8Hz,H^),2.32(lH,dqJ117 = 12.4HzJlll3=6.…”

Section: Resultsmentioning

confidence: 99%

“…$,3a.-Diacetoxy-4$,5a.,11 $-H-eudesman-6a, 12-olide[29].-Mp 175°; [ ]25 -26°(c= 1, CHC13); ir vmax(CHCl3) 1771,1736cm'1; 'HnmriCDCl/b 5.l4(lH,dd,/1=/2 = 3.0Hz,/3=2.9Hz, -3ß),4.77 (1H, dd,/12a=11.7 Hz,/12g=4.9 Hz, H-la),4.60 (1H, dd,/6,"=/67=4.0 Hz, H-6a), 2.38 (1H, q, /" 13 = 7 5. Hz, H-ll), 2.07 (3H, s, Me-AcO), 2.01 (3H, s, Me-AcÓ), 1.29 (3H, d J13," = 7.5 Hz, Me-13), 1.Ó0 (3H, s, Me-14), 0.98 (3H, d J154=6.7 Hz, Me-15); 13C nmr (CDC13)76.8 (C-l), 31.7 (C-2),73.6 (C-3), 31.7 (C-4), 43.2 (C-5), 76.0(C-6), 41.9 (C-7),23.0 (C-8), 34.7 (C-9), 37.0(C-10), 44.5 (C-ll), 180.1 (C-12), 14.4 (C-13),12.6 (C-14),14.6 (C-15), 170.6 (MeCO), 170.5 (MeCO), 21.2 (MeCO), 21.2 (MeCO); cims (CH4) m/z 353 [M+1]+ (57), 293 [M+1 -60]+ (76), 233 [M+l-120]+ (100);anal., found C 64.7, 8.0; Cl9H2806 requires C 64.74, H 8.01%.1 ß,3 $-Diacetoxy-4ß,5ol,1 1 fi-H-eudesman-6fi,l2-olide [30].-Syrup; [a]25D -15°(f=l, CHC13); ir v max(CHC13) 1771,1739cm"1; 'H nmr(CDC13) 4.70 (1H, dd,/65e=/67=4.0 Hz, H-6a), 4.53 (1H, dd, /12a=12.2 HzJ12g=4.6 Hz, H-la),4.51 (1H, ddj1=/2=12.1 Hz,/3=5.4 Hz, H-3a), 2.38 (1H, q, Jn 13=7 7.…”

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Microbial Transformations of 6α- and 6β-Eudesmanolides by Rhizopus nigricans Cultures

García¹,

Garcı́a-Granados²,

Martı́nez³

et al. 1995

J. Nat. Prod.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Microbial Transformations of 6α- and 6β-Eudesmanolides by Rhizopus nigricans Cultures

García¹,

Garcı́a-Granados²,

Martı́nez³

et al. 1995

J. Nat. Prod.

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“…This clearly indicates the presence of one axial hydroxyl group at C-l and another equatorial one at C-3, as expressed by structure 3-We have named this compound 3-^i-erivanin because it is the epimer at C-3 of the known eudesmanolide erivanin, isolated from Artemisia fragrans var. erivanica (12).…”

Section: Resultsmentioning

confidence: 99%

Further New Sesquiterpene Lactones from Artemisia herba-alba subsp. valentina

Sanz¹,

Falcó²,

Marco³

1990

J. Nat. Prod.

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“…The less polar compound was obtained with a yield of 59% and was identified as dihydrosantamarine (3) consistent with its 'H NMR spectrum (6,5.30 (brs, 3-H), 3.93 (dd, J = 9.8 and 11.1 Hz, 6-H), 3.62 (dd, J = 6.7 and 9.8 Hz,lu-H), 1.79 (brs, 15-H)). The more polar component, which was obtained with a yield of 25%, was identified as dihydroreynosin 11.…”

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confidence: 85%

Synthesis of torrentin, dihydrosantamarine, and saussurea lactone from santonin

Blay¹,

Cardona²,

Garcı́a³

et al. 1992

Can. J. Chem.

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. 70, 817 (1992).The synthesis of the eudesmanolide torrentin ( I ) by sensitized photooxygenation of synthetic dihydrosantamarine (3) is reported. Both dihydrosantamarine and dihydroreynosin (11) were obtained from the 1,2-epoxide 9, which, in turn, was prepared from the diselenide 7. An improved procedure for the synthesis of the elemanolide saussurea lactone (4) is also reported.Key words: eudesmanolide, elemanolide, santonin, torrentin, saussurea lactone.GONZALO BLAY, LUZ CARDONA, BEGONA GARC~A et JOSE R. PEDRO. Can. J. Chem. 70, 817 (1992) On rapporte la synthkse de I'eudesmolide de torrentine (1) par une photo-oxygtnation de la dihydrosantamarine de synthkse (3). On a obtenu a la fois la dihydrosantamarine et la dihydroreynosine (11) Torrentin is an eudesmanolide isolated a few years ago ( I ) procedure for the synthesis of saussurea lactone (4) from from Artemisia herba-alba subsp. vulentina, and whose santonin (2). The sesquiterpene lactones, which constitute structure has been revised recently (2). This paper reports on an important group of natural compounds widely distribthe synthesis of torrentin (1) from santonin (2) via a multiuted in the family Compositae, have received much attenstep reaction sequence involving dihydrosantamarine (3) as tion because of their biological activities (3). an intermediate product. It also contributes an improved Dihydrosantamarine (3) was synthesized previously (4) from the dihydrocostunolide (5) and, more recently, by an 1 1-step refunctionalization ( 5 ) of the A ring of santonin (2). We synthesized dihydrosantamarine (3) via a shorter synthetic pathway by applying a new selective transformation of diselenide 7 to the 1,2-epoxide 9. The conversion of dihydrosantamarine (3) into torrentin (1) involved the sensitized photooxygenation of the 3,4-double bond of the former as a key step (6).We used the diol-lactone 6 as starting product, which was prepared from santonin (2) according to Grieco ( 7 ) , i.e., by '~u t h o r to whom correspondence may be addressed. Rinled In Canadahydrogenation and epimerization (8) at C4, formation of the corresponding tosylhydrazone and a Shapiro reaction (9), and, finally, the ozonolysis of the 2,3-double bond followed by reduction with sodium borohydride. Our strategy was based on the synthesis of the 1,2-epoxide 9 from the diol6 by oxidation-elimination of the diselenide 7 and the simultaneous epoxidation of the resulting double bond. Inasmuch as the elimination of the C2 selenoxide should be faster (10) than that of the C3 selenoxide, the yield of epoxide 9 must be more favourable than that of 10 in relation to those obtained by epoxidation (3) of saussurea lactone (4).With the above ideas in mind, we addressed the synthesis Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.245.13.81 on 05/11/18For personal use only.

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Synthesis of erivanin and 1-epierivanin from 1-(α)-santonin

Cited by 15 publications

References 5 publications

Microbial Transformations of 6α- and 6β-Eudesmanolides by Rhizopus nigricans Cultures

Microbial Transformations of 6α- and 6β-Eudesmanolides by Rhizopus nigricans Cultures

Further New Sesquiterpene Lactones from Artemisia herba-alba subsp. valentina

Synthesis of torrentin, dihydrosantamarine, and saussurea lactone from santonin

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