1. Studies on the relative reactivity of three hydroxyl groups in aconitine.
- Author
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She, Xue-Ke, Jian, Xi-Xian, Chen, Dong-Lin, Chen, Qiao-Hong, and Wang, Feng-Peng
- Subjects
CHROMATOGRAPHIC analysis ,ALKALOIDS ,BIOCHEMISTRY ,PHYSICAL & theoretical chemistry ,KETONES ,MASS spectrometry ,PHENOMENOLOGY ,MOLECULAR structure ,NUCLEAR magnetic resonance spectroscopy ,RESEARCH funding ,THIN layer chromatography - Abstract
The relative reactivity of three hydroxyl groups in aconitine toward acetylation, chlorination, sulfonylation, and oxidation has been studied in this paper. The reduction of C-3 ketone and C-15 ketone derivatives of aconitine was also investigated. It was found that (1) the relative reactivity of three hydroxyl groups toward acetylation, chlorination, and sulfonylation is 3-OH>13-OH>>15-OH; (2) 3-OH is much more reactive than 15-OH toward oxidation; and (3) reduction of the carbonyl group at C-3 with NaBH
4 generated a pair of C-3 epimers, while the reduction products of the carbonyl group at C-15 depend largely on the specific reducing agent and the absolute configuration of 16-OCH3 . When the substrate has 16β-OCH3 , its carbonyl group at C-15 can be reduced with NaBH4 to yield exclusively the 15α-OH-containing product. Upon replacement of reducing agent NaBH4 with LiAlH4 , the C-15 carbonyl group can be reduced to yield a pair of C-15 epimers. On the other hand, when the substrate has 16α-OCH3 , C-15 carbonyl group can only be reduced to generate 15α-OH-containing product. [ABSTRACT FROM AUTHOR]- Published
- 2012
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