Minor diterpene glycosides from the leaves of Stevia rebaudiana.
Two new diterpene glycosides in addition to five known glycosides have been isolated from a commercial extract of the leaves of Stevia rebaudiana. Compound 1 (rebaudioside KA) was shown to be 13-[(O-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid 2-O-β-d-glucopyranosyl-β-d-glucopyranosyl ester and compound 2, 12-α-[(2-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid β-d-glucopyranosyl ester. Five additional known compounds were identified, rebaudioside E, rebaudioside M, rebaudioside N, rebaudioside O, and stevioside, respectively. Enzymatic hydrolysis of stevioside afforded the known ent-kaurane aglycone 13-hydroxy-ent-kaur-16-en-19-oic acid (steviol) (3). The isolated metabolite 1 possesses the ent-kaurane aglycone steviol (3), while compound 2 represents the first example of the isomeric diterpene 12-α-hydroxy-ent-kaur-16-en-19-oic acid existing as a glycoside in S. rebaudiana. The structures of the isolated metabolites 1 and 2 were determined based on comprehensive 1D- and 2D-NMR (COSY, HSQC, and HMBC) studies. A high-quality crystal of compound 3 has formed, which allowed the acquisition of X-ray diffraction data that confirmed its structure. The structural similarities between the new metabolites and the commercially available stevioside sweeteners suggest the newly isolated metabolites should be examined for their organoleptic properties. Accordingly rebaudiosides E, M, N, O, and KA have been isolated in greater than gram quantities.
Ironstone Separations, Inc. , Etta, Mississippi 38627, United States.
Mohamed A
MA
Ibrahim
Douglas L
DL
Rodenburg
Kamilla
K
Alves
Frank R
FR
Fronczek
James D
JD
McChesney
Chongming
C
Wu
Brian J
BJ
Nettles
Sylesh K
SK
Venkataraman
Frank
F
Jaksch
D045786:Diterpenes, Kaurane / Q000032:analysis / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D005960:Glucosides / Q000032:analysis / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D008910:Minnesota; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D018515:Plant Leaves / Q000737:chemistry; D036625:Stevia / Q000737:chemistry*; D013549:Sweetening Agents / Q000032:analysis / Q000737:chemistry / Q000302:isolation & purification / Q000494:pharmacology
D045786:Diterpenes, Kaurane; D005960:Glucosides; D013549:Sweetening Agents; C012043:stevioside; C012042:steviol