@article{77a8dc21395b484f947f991e31a42d7b,
title = "Cardenolide glycosides from the roots of mandevilla pentlandiana",
abstract = "From the roots of Mandevilla pentlandiana 13 cardenolide-type compounds were isolated. Besides free aglycones digitoxigenin and oleandrigenin, the structures of mono-, tri-, tetra- and pentaglycosides of both genins were characterized by means of chromatographic and spectroscopic methods.",
keywords = "Apocynaceae, cardenolides, cardiotonic glycosides., Mandevilla pentlandiana, roots",
author = "Cabrera, \{Gabriela M.\} and Deluca, \{M{\'o}nica E.\} and Seldes, \{Alicia M.\} and Gros, \{Eduardo G.\} and Oberti, \{Juan C.\} and Janeen Crockett and Gross, \{Michael L.\}",
note = "Funding Information: H-16), 3.35 (3H, s, MeO), 1.84 (3H, s, AcO), 1.64 (3H, d, J (2). {\textquoteleft}HNMR (pyridine-d,):6 6.12( IH, br s, H-22), 5.31 =6 Hz, H-6{\textquoteright}), 1.10 (lH, s, H-18), 0.88 (3H, s, H-19). (lH,brd,J=18Hz,H-21),5.18(1H,brd,J=8Hz,H-I{\textquoteright}), 13C NMR see Table 2. 5.09( lH, d, .I=8 Hz, H-l{\textquoteright}), 5.02( lH, br d, 5=18 Hz, H-Oleandrigenin-3-0-[r-L-rhamnopyranosyl-( 1-6)-p-\textasciitilde{}-21),4 .82( lH, d, 5=8 Hz, H-l”), 3.59 (3H, s, MeO), 2.77 glucopyranosyl-( 1-4)-p-D-ghXopyranosyl-( l-4)-b-D-cyma- (lH, m, H-17), 1.64( 3H, d, 5=6 Hz, H-6{\textquoteright}), 0.99( 3H, s, H-ropyranoside] (9). Solid, [cc-Jo-10 o (MeOH; c 0.25). UV 18),0 .87( 3H, s, H-19). 13CNMR seeT able 2. 1,,, (8): 220 (800). FABMS m/z: 908 [M + Na + 11+ (lOO), Digitoxigenin-3-O-[B-D-g\textasciitilde{}UcOpyrcmOSy\textasciitilde{}1-(- 6)-/3-D-\& 867 (22), 720 (15), 414 (12), 372 (24), 133 (85). {\textquoteleft}HNMR copyranosyl-(l-4)-\textasciitilde{}-D-diginopyrunosyl-(l-4)-\textasciitilde{}-D-cymuro- (pyridine-d,): 66.33 (lH, br s, H-22), 5.67 (lH, ddd, J= 10, pyranosyl-(1-4)-P-D-cymaropyranoside] (13). Solid, mp 10 and 2 Hz), 5.50 (lH, br s, H-l”{\textquoteleft}), 5.41 (lH, br d, J= 18 16\&165”, [a\&, -5” (MeOH, c 0.25).U V A,,,,,( E):2 26 Hz, H-21),5 .23( lH, br d, J= 18H z, H-21),5 .19( lH, br d, (2900).F ABMS-CAD-MS of [M+H]+: 1113[ M+H J=8 Hz, H-1{\textquoteright}),4.89(1H,d , J=8 Hz, H-1”),4.45(1H,dd,J -H,O]+ (18),1 099[ M+H-MeOH]+ (lOO),9 69 [M = 9 and 2 Hz, H-3{\textquoteright}), 3.69( lH, dd, J = 9 and 2 Hz, H-4{\textquoteright}), +H-162]+(3),937[969-MeOH]+(2),663[M+H-2 3.65 (3H, s, MeO), 3.37 (lH, d, .I= 10H z, H-17), 1.84( 3H. x 162]+( 3), 519 [M+H-2x 162-144]+ (6), 375 [M s, AcO), 1.63( 6H,d, J =6 Hz, H-6{\textquoteright} and 6”{\textquoteleft}), 1.06( 3H, s, H-+H-2 x 162-3 x 144]+ (2). {\textquoteleft}HNMR (pyridine-d,): 18),0 .87( 3H, s, H-19). r3CNMR seeT able 2. 66.12(1H,brs,H-22),5 .16(1H,b rd,J=8Hz,H-1{\textquoteright}), 5.04 Digitoxigenin-3-O-[B-D-ghKopyranosy/-( 1-6)-/I-glucopy-(lH, d, 5=8 Hz, H-l{\textquoteright}), 5.02( IH, br d, 3=18 Hz, H-21), ranosyl-I(- 4)-B-D-cymaropyranoside] (10) (echujin [ 141). 4.80(1H,d,5=9Hz,H-l”),3.59(3H,s,MeO),3.36(3H,s, Solid, [r]n -7” (MeOH; c 0.35). UV 1,.x (E): 225 MeO),2.78(1H,m,H-17),1.64(3H,d,3=6Hz,H-6{\textquoteright}),0.99 (1800).F ABMS m/z: 881.3915C, ,,Hs,O,,K, requires (3H, s, H-18),0 .87( 3H, s, H-19). r3C NMR seeT able 2. 881.3937F.A BMS-CAD-MS of [M+H-J+: 825 [M +H Mild hydrolysis. The glycoside( 5-10 mg)w ash eateda t -HzO]+ (31), 811 [M+H-MeOH]+ (lOO),6 81 [M 60” in 0.25M H,SO, (EtOH or dioxane)in a sealedt ube +H-162]+ (8), 649 [681-MeOH]{\textquoteright} (12),5 19 [M+H for 1 hr. After cooling,t her eactionm ixturew ase xtracted -2x162]+ (6), 375 [M+H-2x162-1441{\textquoteright} (14). with CH,CI,, washedw ith H,O, dil. NaHCO, and Hz0 {\textquoteleft}H NMR (pyridine-d,):6 6.12( lH, br s, H-22),5 .31( lH, br and evapda t red.p res.T he aq.p hasew asn eutralizedw ith d, .I=18 Hz, H-21), 5.19( lH, br d, J=9 Hz, H-l{\textquoteright}), 5.09 satd NaHCO, soln and evapd. (lH, d, 5=8 Hz, H-l”{\textquoteleft}), 5.03( lH, br d, 5=18 Hz, H-21), Strong hydrolysis. The samplew ash eateda t 80” in 6\% 4.83( iH, d, J=8 Hz, H-l”), 4.45( lH, m, H-3{\textquoteright}), 3.67( lH, aq. HCI for 2 hr. After cooling the reactionm ixturew as dd, J=9 and 2 Hz, H-4), 3.62( 3H, s, MeO), 2.77( lH, m, worked-upa s above. H-17), 1.57 (3H, d, J= 6 Hz, H-6{\textquoteright}), 1.00( 3H, s, H-18),0 .87 Preparation ofacetylated alditols. To thes ugar( 1m g)i n (3H, s, H-19). 13CNMR seeT able 2. Hz0 (1 ml) one drop of ammonia and NaBH, (10m g) Digitoxigenin-3-O-[cr-L-rhamnopyranosyl\textasciitilde{}l-6\textasciitilde{}\textasciitilde{}-D-g\textasciitilde{}u- werea ddedT. he mixturew asl eft at room temp.f or 12h r. copyrunosyl-(l-4)-/I-D-cymaropyranoside] (11).S olid, [a]n Dil. HCI wasa ddedt o pH 6 and them ixturew ast akent o -3 o (MeOH; c 0.20).U V I.,,,,, (c):2 20 (5100)F. ABMS dryness.T he alditols werea cetylatedb y treatmentw ith m/z: 850 [M+Na+l]{\textquoteright} (lOO),5 51( 30) 386( 18),3 75( ll), Ac,O-pyridine (1: 1) at loo” for 1 hr and treateda s 145( 36).{\textquoteleft} HNMR (pyridine-d,):6 6.13( lH, br s, H-22), describedf or the generala cetylationr eaction.G C ana-5.49(1H,brs,H-1”{\textquoteleft}),5.31(1H,brd,J=18Hz,H-21),5.18 lysis of the derivativesw ere performedo n a capillary (lH, br d, J=8 Hz, H-l{\textquoteright}), 5.03( lH, br d, J= 18H z, H-21), column SP 2330( 200-250”,l o” min-{\textquoteleft}). 4.88( lH, d, J=8 Hz, H-l”), 4.46( lH, m, H-3{\textquoteright}), 3.69( lH, dd, J=9 and 2 Hz, H-4{\textquoteright}), 3.64 (3H, s, MeO), 2.77 (lH, m, Acknowledgements-We thank Drs T. Yamauchi H-17), 1.63( 6H, d, .I = 6 Hz, H-6 and 6”{\textquoteleft}k 1.00( 3H, s, H-(Fukuoka University,Japan)and P. Junior (Universitlt 18), 0.87 (3H, s, H-19). 13CN MR see Table 2. After Dusseldorf)for samples,and Drs L. K. Larsen and F. hydrolysis of 25 mg 11 (see mild hydrolysis)t he sugar Caplan (Universityof Hawaii) for pharmacologicatlests. mixture was separatedb y prep. TLC (CH,Cl,-MeOH, We are also indebtedtoUMYMFOR for spectrandto 20\%) yielding a disaccharidea nd a trisaccharideT. he CONICET (Argentina)forpartial financial support. latterw asf urtherh ydrolysedin mild conditionsy ielding D-cymarose[ alo +47” (MeOH; c 0.036)[ 21] and the disaccharideo btainedb efore.T his one wash ydrolysedin strongerc onditions (sees trong hydrolysis)a ffordingD - glucose and L-rhamnose( GC of alditol acetatesa nd optical rotation). \textasciitilde{}igitoxigenin-3-O-[\textasciitilde{}-D-g\textasciitilde{}ucopyranosy\textasciitilde{}-(l-6)-\textasciitilde{}-D-g\textasciitilde{}u-copyranosy\textasciitilde{}-(l-4\textasciitilde{}\textasciitilde{}-D-cymaropyranosy\textasciitilde{}-(:i\textasciitilde{})-\textasciitilde{}-D-Cymaropyranoside] (12). Solid, [a\&, -25{\textquoteright} (MeOH; c 0.15).U V kX n (e): 224 (3500). FABMS m/z: 1025.4675, C,,H,,O,,K, requires 1025.4734. FABMS-CAD-MS of [M+H]+: 969 [M+H-H,O]+ (ll), 955 [M+H -MeOH]+ (lOO), 825 [M+H-162]+ (2), 793 [825 -MeOH]+ (3), 663 [M+H-2x 162]+ (l), 519 [M+H -2x 162-144-J+ (5), 375 [M+H-2x 162-2x 144-J+",
year = "1993",
month = mar,
doi = "10.1016/S0031-9422(00)95101-X",
language = "English",
volume = "32",
pages = "1253--1259",
journal = "Phytochemistry",
issn = "0031-9422",
number = "5",
}