(13)C, (15)N CPMAS NMR and GIAO DFT calculations of stereoisomeric oxindole alkaloids from Cat's Claw (Uncaria tomentosa).
Oxindole alkaloids, isolated from the bark of Uncaria tomentosa [Willd. ex Schult.] Rubiaceae, are considered to be responsible for the biological activity of this herb. Five pentacyclic and two tetracyclic alkaloids were studied by solid-state NMR and theoretical GIAO DFT methods. The (13)C and (15)N CPMAS NMR spectra were recorded for mitraphylline, isomitraphylline, pteropodine (uncarine C), isopteropodine (uncarine E), speciophylline (uncarine D), rhynchophylline and isorhynchophylline. Theoretical GIAO DFT calculations of shielding constants provide arguments for identification of asymmetric centers and proper assignment of NMR spectra. These alkaloids are 7R/7S and 20R/20S stereoisomeric pairs. Based on the (13)C CP MAS chemical shifts the 7S alkaloids (delta C3 70-71ppm) can be easily and conveniently distinguished from 7R (deltaC3 74.5-74.9ppm), also 20R (deltaC20 41.3-41.7ppm) from the 20S (deltaC20 36.3-38.3ppm). The epiallo-type isomer (3R, 20S) of speciophylline is characterized by a larger (15)N MAS chemical shift of N4 (64.6ppm) than the allo-type (3S, 20S) of isopteropodine (deltaN4 53.3ppm). (15)N MAS chemical shifts of N1-H in pentacyclic alkaloids are within 131.9-140.4ppm.
Paradowska
Katarzyna
K
Faculty of Pharmacy, Medical University of Warsaw, 02-097 Warsaw, Banacha 1, Poland.
Wolniak
Michał
M
Pisklak
Maciej
M
Gliński
Jan A
JA
Davey
Matthew H
MH
Wawer
Iwona
I
D000470:Alkaloids / Q000737:chemistry*; D020948:Cat's Claw / Q000737:chemistry*; D002725:Chloroform / Q000737:chemistry; D003903:Deuterium / Q000737:chemistry; D007211:Indoles / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D000078183:Oxindoles; D011789:Quantum Theory; D013237:Stereoisomerism
D000470:Alkaloids; D007211:Indoles; D000078183:Oxindoles; C022960:2-oxindole; D002725:Chloroform; D003903:Deuterium