TY - JOUR
T1 - Formation of Samin Diastereomers by Acid-Catalyzed Transformation of Sesamolin with Hydrogen Peroxide
AU - Tsai, Hsin Ya
AU - Lee, Wei Ju
AU - Chu, I. Hsuan
AU - Hung, Wei Ching
AU - Su, Nan Wei
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/6/10
Y1 - 2020/6/10
N2 - The conversion of sesame lignans is of interest because the derived products may have potential applications. Here, in investigating the transformation of sesamin and sesamolin, main endogenous sesame lignans in sesame seeds, in both acidic aqueous and anhydrous systems, 7R,7'S-samin was identified as one of the major products of sesamolin in both systems catalyzed with common inorganic acids, but sesaminol was not generated. In investigating the effect of different oxidizing agents on the acid-catalyzed conversion of sesame lignans, 7R,7'S-samin was still the major product of sesamolin, whereas sesamolin as well as 7R,7'S-samin stereoselectively rendered 7R,7'R-samin in the presence of hydrogen peroxide. Hydrogen peroxide may play a role in stabilizing the transitional oxonium ions, derived from acid hydrolysis of sesamolin or 7R,7'S-samin by forming a seven-membered ring intermediate through hydrogen bonding, to consequently produce 7R,7'R-samin as the final product.
AB - The conversion of sesame lignans is of interest because the derived products may have potential applications. Here, in investigating the transformation of sesamin and sesamolin, main endogenous sesame lignans in sesame seeds, in both acidic aqueous and anhydrous systems, 7R,7'S-samin was identified as one of the major products of sesamolin in both systems catalyzed with common inorganic acids, but sesaminol was not generated. In investigating the effect of different oxidizing agents on the acid-catalyzed conversion of sesame lignans, 7R,7'S-samin was still the major product of sesamolin, whereas sesamolin as well as 7R,7'S-samin stereoselectively rendered 7R,7'R-samin in the presence of hydrogen peroxide. Hydrogen peroxide may play a role in stabilizing the transitional oxonium ions, derived from acid hydrolysis of sesamolin or 7R,7'S-samin by forming a seven-membered ring intermediate through hydrogen bonding, to consequently produce 7R,7'R-samin as the final product.
KW - acid-catalyzed transformation
KW - furofuran lignans
KW - hydrogen peroxide
KW - samin diastereomers
KW - sesame oil
KW - sesamolin-derivative
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U2 - 10.1021/acs.jafc.0c01616
DO - 10.1021/acs.jafc.0c01616
M3 - Article
C2 - 32396352
AN - SCOPUS:85086346298
SN - 0021-8561
VL - 68
SP - 6430
EP - 6438
JO - Journal of Agricultural and Food Chemistry
JF - Journal of Agricultural and Food Chemistry
IS - 23
ER -