561-05-7Relevant articles and documents
Studies on the relative reactivity of three hydroxyl groups in aconitine
She, Xue-Ke,Jian, Xi-Xian,Chen, Dong-Lin,Chen, Qiao-Hong,Wang, Feng-Peng
experimental part, p. 665 - 677 (2012/10/08)
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 NaBH4 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 16-OCH3, its carbonyl group at C-15 can be reduced with NaBH4 to yield exclusively the 15-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 16-OCH3, C-15 carbonyl group can only be reduced to generate 15-OH-containing product.
