Bisbenzylisoquinoline Alkaloids from Cyclea barbata

Abstract

Continuing studies of the alkaloidal fraction from the roots of Cyclea barbata afforded two new bisbenzylisoquinoline alkaloids, namely, (-)-2'-norlimacine [1] and (+)-cycleabarbatine [2]. The known (+)-tetrandrine-2'-beta-N-oxide [3], for which the configuration of the N-oxide function is now assigned, was identified, as were (+)-berbamine, (-)-repandine, (+)-cycleanorine, (+)-daphnandrine, (-)-curine, (+)-coclaurine, and (-)-N-methylcoclaurine.

Bisbenzylisoquinoline Alkaloids

“…)6,7,8,11*,12-6,7* [7][8][9][10][11][12] mp: yellow oil 76 [R] 25 D: 0.0°(c 0.002, CHCl3) 76 65 (q, NMe-2′), 55.64 (q, OMe-6′), 55.72 (q, OMe-6) 76 EIMS: M + 608 (1), 400 (3), 298 (100), 266 (15), 206 (29), 161 (20), 132 (7) (76), 620 (19), 619 (36), 591 (3), 341 (15), 340 (68), 339 (2), 298 (12), 297 (14), 295 (49), 294 (8), 282 (20), 190 (14), 189 (100), 187 (14), 159 (48) 79 CD: 0 (307), -2.6 sh (294), -4.7 (286), -3.2 (281), -3.4 (278), -0.9 (254), -9.8 (240), 0 (235), positive tail below 230 79 source: Cyclea atjehensis (Menispermaceae) 79 401 Curicycleatjine C37H36O7N2: 620.2523 type XXI (S,R) 6,7,8*,11 (65), 296 (10), 295 (30), 284 (35), 189 (96), 187 (35), 159 (65) 79 CD: 0 (312), -2.4 sh (294), -3.9 (285), -2.6 (282), -3.1 (279), 0 (253), -9.4 (241), 0 (235) 79 source: Cyclea atjehensis (Menispermaceae) 79 402 Cycleabarbatine C37H40O6N2: 608.2886 type VIII (R,S) 6,7,8*,11 [7][8][9][10][11][12] mp: amorphous residue 75 [R] (19), 590 (3), 588 (8), 574 (3), 399 …”

“…69 1 H NMR: NMe 2.61 (6H, N-2 and N-2′); OMe 3.54 (C-7′), 3.71 (C-11′), 3.79 (C-12), 3.80 (C-6), 3.82 (C-6′); AlH 2.5-3.5 (14H, complex, ring CH2); ArH 5.91 (H-8′), 6.22 (H-8), 6.53 (H-5), 6.54 (1H, d, J ) 2.0 Hz, H-10′), 6.66 (2H, d, J ) 8.5 Hz, H-11 + H-13), 6.66 (1H, s, H-5′), 6.71 (1H, dd, J ) 2.0, 8.3 Hz, H-14′), 6.82 (1H, d, J ) 8.3 Hz, H-13′), 6.89 (2H, d, J ) 8.5 Hz, H-10 + H-14) 69 EIMS: 639 [M + 1] + (0.4), 638 [M] + (0.1), 518(7), 517(20), 326 (100), 312(12), 296 (8), 206(75), 121(18) …”

“…(-)-Norcycleanine (C37H40O6N2: 608.2886) Stephania cepharantha (Menispermaceae) 28 133 (-)-Curine (C36H38O6N2: 594.2730) Cyclea barbata (Menispermaceae),7 Stephania epigaea (Menispermaceae)32 152 Cocsoline (C34H32O5N2: 548.2311) Cocculus pendulus (Menispermaceae)55 153 Cocsuline (C35H34O5N2: 562.2468) Cocculus pendulus (Menispermaceae),55,58 Pachygone dasycarpa (Menispermaceae) 9 155 12′-O-Demethyltrilobine (C34H32O5N2: 548.2311) Cocculus pendulus (Menispermaceae)55 Reviews…”

“…[R]D: +311°5 5 423 2′-Norlimacine C36H38O6N2: 594.2730 type VIII (R,R) 6,7,8*,11 + ,12-6,7*, 12 + mp: amorphous residue 7 [R]D: -125°(c 0.13, CHCl3) (80), 592 (11), 579 (19), 416 (13), 368 (12), 367 (40), 353 (18), 192 (11) 7 source: Anisocycla jollyana (Menispermaceae) 36 , Cyclea barbata (Wall) Miers (Menispermaceae) 3 (q, NMe-2′), 42.6 (q, NMe-2), 55.9 (q, OMe-6), 55.9 (q, OMe-6′) 69 EIMS: 597 [M + 1] + (0.7), 596 [M] + (0.1), 490 (10), 489 (32), 298 (40), 297 (11) 36 VI isotrilobine (157) 36 XXIII limacine (64) 36 VIII limacine 2′β-N-oxide (317) 36 VIII limacusine 2′β-N-oxide (413) 36 VI 2-norlimacine (336) 36 VIII 2′-norlimacine (336) 36 VIII trilobine (163) 36 XXIII 16 VIII berbamunine (1) 16 I obaberine (46) 16 VI oxyacanthine (48) 16 VI Berberis integerrima Bge. (Berberidaceae) L oxyacanthine (48) L berbamunine (1) 18 I 2′-N-methylberbamine (66a) 18 VIII O-methylthalicberine (95) 18 XI oxyacanthine (48) 70 XXIII Cocculus pendulus (Forsk) Diels (Menispermaceae) L, St cocsiline (396) 55 XXIV cocsilinine (397) 55 XXIV cocsoline (152) 55 XXIII cocsuline (153) 55,58 XXIII cocsulinine (164) 55 XXIV 12′-O-demethyltrilobine (155) 55 XXIII O,O-dimethylcocsulinine (164) 55 XXIV hernandezine (81) 58 I...…”

“…majus (Ranunculaceae) 41 49 Repandine (C 37 H 40 O 6 N 2 : 608.2886) Cyclea barbata (Menispermaceae) 7 52a Thaligosine (C 38 H 42 O 7 N 2 : 638.2992) Thalictrum foetidum (Ranunculaceae), T. minus var. majus 41 52b Thaligosinine (C 39 H 44 O 7 N 2 : 638.2992) Thalictrum foetidum (Ranunculaceae), T. fargesii 53 Thalisopidine (C 37 H 40 O 7 N 2 : 624.2836) Thalictrum fargesii (Ranunculaceae), T. isopyroides 55 Thalrugosaminine (C 39 H 44 O 7 N 2 : 638.2992) Thalictrum foetidum (Ranunculaceae) 49 56 Atherospermoline (C 36 H 38 O 6 N 2 : 594.2730) Pachygone dasycarpa (Menispermaceae) 9 57 Berbamine (C 37 H 40 O 6 N 2 : 608.2886) Berberis aggregata (Berberidaceae), B. dictyoneura (Berberidaceae), B. francisci-ferdinandi , B. heterobotrys , B. iliensis , B. pseudothunbergii , B. sibirica , B. vulgaris , Cyclea barbata (Menispermaceae), Stephania cepharantha (Menispermaceae) 28,31,33 60 Cycleanorine (C 37 H 40 O 6 N 2 : 608.2886) Cyclea barbata (Menispermaceae) 7 61 Fangchinoline (C 37 H 40 O 6 N 2 : 608.2886) Pachygone dasycarpa (Menispermaceae), Stephania tetrandra (Menispermaceae), Strychnopsis thouarsii (Menispermaceae) …”