Chapter 7 Bisbenzylisoquinoline and Related Alkaloids

Bisbenzylisoquinoline Alkaloids

“…(43), 607 (32), 501 (6), 382 (31), 381 (100), 367 (34), 192 (18), 191 (62), 174(39), 168(52) (24) SOURCES: Daphnandra johnsonii (Monimiaceae) ( (24) [a]"n: +212°(CHC1S) (24) UV: 280(3. iV,0-Dimethylapateline (7V-Methylapateline+CH3Ni) (Same as -Me thy 1telobine) (24) 208. N-METHYLNORAPATELINE C34H3,03N,: 548.2311 Type XXIII (R,S) 6*,7+,llt,12-6,7*,8+,12t IR: 3450, 1585, 1500, 1445, 1350, 1270, 1210, 1108, 870, 748, 658 (24) 'HNMR: (CDC13+CD30D) (NCH3 2.44, 2.49; A1H 2.20-4.10(14); ArH 5.89(H8), 6.27(H5), 6.39(H51), 6.60(H10), 6.77-7.20 (6) (24) MS: M+ 548 (found 548.2307) (24), 336 (38), 335 (100), 321 (32), 168(46) (24) SOURCES: Daphnandra johnsonii (Monimiaceae) (24) DERIVATIVES: 7V,0-Dimethylapateline (N-Methylnorapateline+CHjNi) ( (44) [ ]« : +109°(c=0.22, CH3OH) (44) UV: 280(4.02), 285(sh) (4.01) (44) 'HNMR: NCH3 2.49, 2.53; OCH3 3.60, 3.63, 3.78, 3.80, 3.83; ArH 6.10(H8), 6.16(H8'), 6.53(H5), 6.56(H51), 6.6-7.2 (7) (44) MS: M+ 638«1), 206 (100), 191 (9), 190(9) (44) CD: (3.4 x 10" *M, CH,OH) 228(+75,000), 250(0), 270(0), 287(+15,500), 300(0) (44) SOURCES: Thalictrum minus race B (Ranunculaceae) (44) PREPARATION: Via methylation (CH,N,) of thalibrine (TLC, SP ROTN, UV, IR, 'HNMR, CD) (44) DERIVATIVES: Birch Reduction (Na/NH3) afforded ( 5)-(+)-<3-methylarmepavine and…”

“…N'-NORHERNANDEZINE C38H4207N2: 638.2992 MP: Amorphous (37) TLC: 0.46 (Silica Gel G; C6H6-(CH3)2CO-NH4OH [10:10:0.4] ) (37) [a]»n: +143°(c = 0.28, CHsOH) (37) 'HNMR: NCH3 2.30; OCHa 3.30, 3.35, 3.79, 3.82, 3.93; ArH 6.01 (H81), 6.87(H51), ABXY pattern at 6.36, 6.81 (dd each, 1H each, J=2,8 Hz) and 7.14, 6.37(dd, 1H each, J=2,8 Hz), ABC multiplet at 6.S-6.9 (37) MS: M+ 638(9), 623(4), 607(2), 501(1), 460 (13), 425 (15), 411 (34), 397 (22), 381 (6), 238 (10), 234 (11), 222 (8), 220( 14), 213 (58), 206(100), 198 (22), 192 (27), 191 (26), 190 (18), 183 (11), 178 (10), 176 (12), 174(26), 160(20) (37) CD: (4.4 x 10-3M, CHsOH) 218(+169,000), 241(0), 247(-31,400), 261(0), 266(sh) (+4,000), 287(+17,300), 320(0) (37) SOURCES: Thalictrum rochebrunianum (Ranunculaceae) (37) PREPARATION: Via reduction (NaBH4-CH3OH) of thalisimine to afford epinorhernandezine and norhemandezine which were separated via column chromatography (37) Type I (5,5) SOURCES: Limaciopsis loangensis (Menispermaceae) (28) DERIVATIVES: Isotetrandrine (2'-Norisotetrandrine+CHjO+NaBH4) (28) 214. A'-NORTHALIBRUNINE C38H"08Ns: 654.2941 MP: 158-161°( 37); Amorphous (47) TLC: 0.43 (Silica Gel G; C6H6-(CH3),C0-NH40H [10:10:0.4] ) (developed twice) (37) [<*]«°d: +79°(c = 0.16, CH3OH) (37) [a]n: +95°(c = l, CHOI,) (47) UV: ( , , ) (30), 623 (12), 476 (7), 411 (40), 397 (27), 222 (12), 206…”

“…(42) TLC: 0.94 (Silica Gel G; C3H8-(CH3)sCO-NH4OH [10:10:0.3]) (42) 'HNMR: NCH3 2.61; OCH3 3.54, 3.74, 3.86, 3.91; OCH,CH, 0.73(t, J=7 )(42) MS: M+652(40), 637(7), 621(8), 426(27), 425(100), 411(7), 222(8), 213(63), 206(10), 204(17), 198(10), 192(7), 190(17), 188(3)'(42) Birch reduction (Na/NH3) afforded (5)-(+)-6,4 '-dimethoxy-7-e thoxy-benzyl-l ,2,3,+ tetrahydroisoquinoline and (5)-(+)-5-hydroxyarmepavine(42) T h i s c o n t e n t i s o n l y l i c e n s e d f o r c o n s u m p t i o n b y A u t h o r i z e d U s e r s a f f i l i a t e i n d i v i d u a l n o t d i r e c t l y a s s o c i a t e d w i t h s c i t e i s p r o h i b i t e d .…”

“…MS: M+ 594(2), 578(10), 352(7), 351(29), 176(4), 57(100) (52) SOURCES: Triclisia gilletii (Menispermaceae) (52) DERIVATIVES: Gilletine diastereoisomer (Isogilletine-N-Oxide+HiSO,) (UV', IR, *HMNR, MP) (52) 205. ISOTHALICBERINE C,7H40O,Ns: 608.2886 Type XI (R,S) 6,7,8*,11+,12-6*,7,12+ MP: 153-155°( C,H"-CHC1,) (38) Mmd: -205°(c=0.4, CHC1,) (38) UV: (CHjCH,OH) 284(3.98) (38) IR: 3575, 2875 (38) •HNMR: NCH, 2.33(N2), 2.57(N2'); OCH, 3.45(C7), 3.75(C7'), 3.80(C6); ArH 5.44(d, 7= 2 Hz), 6.15, 6.4, 6.52-6.82(5), 7.03(d, 7=2 Hz), 7.55(dd, 7=2 and 8 Hz) (38) MS: M+ 608(70), 396(20), 395(61), 381(13), 205(9), 204(33), 198(100), 191(9), 190(28), 175(43), 174(46)(38) …”

Spectral Characterisation and Antiplasmodial Activity of Bisbenzylisoquinolines from Isolona ghesquiereina

“…No previous report either on the ethnomedical uses or on scientific investigations of this species, which grows in the south-west rainy forest of Madagascar, appears in the literature. Phytochemical investigation of the crude alkaloid extract has resulted in the characterisation of three known bisbenzylisoquinoline (BBIQ) alkaloids, identified as (±)-curine, chondrofoline and isochondodendrine (1) largely by interpretation of their 2D NMR spectral data. In the present paper, we wish to report the total spectral characteri-sation of the three BBIQ and their biological evaluation in terms of antiplasmodial activity.…”