title: Studies on the relative reactivity of three hydroxyl groups in aconitine.
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-OCH(3). When the substrate has 16β-OCH(3), its carbonyl group at C-15 can be reduced with NaBH(4) to yield exclusively the 15α-OH-containing product. Upon replacement of reducing agent NaBH(4) with LiAlH(4), 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-OCH(3), C-15 carbonyl group can only be reduced to generate 15α-OH-containing product.
authors.affiliation: Department of Chemistry of Medicinal Natural Products, West China College of Pharmacy, Sichuan University, Chengdu, 610041, China.
authors.forename: Xue-Ke
authors.initials: XK
authors.lastname: She
authors.forename: Xi-Xian
authors.initials: XX
authors.lastname: Jian
authors.forename: Dong-Lin
authors.initials: DL
authors.lastname: Chen
authors.forename: Qiao-Hong
authors.initials: QH
authors.lastname: Chen
authors.forename: Feng-Peng
authors.initials: FP
authors.lastname: Wang
mesh_terms: D000157:Aconitine / Q000737:chemistry* / Q000494:pharmacology; D017665:Hydroxyl Radical / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D007659:Ketones; D017665:Hydroxyl Radical; D000157:Aconitine