Berberis lycium

Aniba canelilla (Lauraceae) eje 71,1128 93 Annona purpurea (Annonaceae) jnp 61,1457 98 Aristolochia chilensis (Aristolochiaceae) fit 61,190 90 Berberis lycium (Berberidaceae) daib 44,1458 83 Corydalis claviculata (Papaveraceae) jnp 53,1280 90 Croton bonplandianus (Euphorbiaceae) tet 37,3175 81 Desmos tiebaghiensis (Annonaceae) jnp 45,617 82 Guatteria sagotiana (Annonaceae) jnp 49,1078 86 Isolona zenkeri (Annonaceae) pm 50,23 84 Liriodendron tulipifera (Magnoliaceae) cnc 11,829 75 Litsea cubeba (Lauraceae) jea 667,322 94... 

Chenabine (99), C37H40N207, along with its 7 -0-demethyl analog, jhelu-mine (100, Section II,C,49), was isolated from Berberis lycium Royle (Ber-beridaceae). Chenabine shows [ajjy5 +40° (c 0.18, MeOH), IR 1680 cm 1 (aromatic aldehyde), NMR (CDC13) 8 3.25 (7 -OMe), 5.23 (s, H-8), MS m/e 624 (M+, 0.2%), 397 (base), and 227 (4, both from cleavage at a). The UV spectrum shows a bathochromic shift as well as a hyperchromic effect with base, typical of a p-hydroxybenzaldehyde. 

Punjabine (156, see Section II,C,38), C35H32N207, [a] 5 -40° (c 0.48, MeOH), from Berberis lycium Royle (Berberidaceae), has IR absorptions at 1620 and 1645 cm -1 (lactam) and 1690 cm 1 (aromatic aldehyde) and shows a large bathochromic shift, indicative of a p-hydroxybenzaldehyde. The NMR spectrum is quite similar to that of gilgitine (155, Section II,C,38), except for the phenolic ring, which shows an aldehyde (8 9.74) rather than a carbomethoxy (8 3.81) resonance. The CD spectrum displays a positive Cotton effect, as expected for the (5) configuration (95). 

In addition to gilgitine (Section II,C,38) and punjabine (Section II,C,97), a third new secobisbenzylisoquinoline, (+)-sindamine (289), C37H38N2Og, [a] >5 +38° (c 0.04, MeOH), was isolated from Berberis lycium Royale (Berberida-ceae) as an amorphous material, IR (CHC13) 1605 and 1645 (lactam) and 1695... 

The secobisbenzylisoquinoline sindamine (270) from Berberis lycium (Berberidaceae) is the only representative of this very small subgroup. The rotation for naturally occurring sindamine was not reported, but sindamine prepared from berbamine had a positive rotation, even though the C( I) atom of berbamine is of the K stereochemistry. 

Products of such oxidative fission of bisbenzylisoquinolines with one, two and three diphenyl ether linkages have been found to be natural products forming a small sub-group of secobisbenzylisoquinoline alkaloids. Those so far identified are karakoramine (68), jhelumine (69, R=H), chenabine (69, R=Me), sindamine (70), punjabine (73, R =H, R =CH0) and gilgi-tine (73, R =H, R =C00Me), isolated from Berberis lycium (J.E. Leet et al.. Heterocycles, 1982, J9, 2355 1983, 425),... 

Scoulerine (145 R = H), the main constituent of Argemone albiflora, had not been previously obtained from Argemone species.The previously named alkaloid HF 1 isolated from Hunnemannia fumariaefolia was found to be identical with ( —)-scoulerine. The co-occurrence of (— )-tetrahydropalmatine (145 R = Me) and (-f )-armepavine in Argemone turnerae has been established for the first time.The isolation and characterization of two artefact alkaloids, berberine chloroform (146 R + R = CH2 R = H,CCl3) and palmatine chloroform (146 R = R = Me, R = H,CCl3), from Berberis lycium have... 

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