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| Napelline-type C20-diterpenoid alkaloid iminiums from an aqueous extract of “fu zi”: Solvent-/base-/acid-dependent transformation and equilibration between alcohol iminium and aza acetal forms |
| Xian-Hua Meng, Zhi-Bo Jiang, Cheng-Gen Zhu, Qing-Lan Guo, Cheng-Bo Xu, Jian-Gong Shi |
| State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China |
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Abstract Three new napelline-type C20-diterpenoid alkaloids, named aconicarmichinium A and B trifluoroacetates (1 and 2) and aconicarmichinium C chloride (3), were isolated from an aqueous extract of “fu zi”, the lateral roots of Aconitum carmichaelii. Their structures were elucidated by extensive spectroscopic data analysis. Compounds 1-3 represent the first examples of napelline-type C20-diterpenoid alkaloid alcohol iminiums, of which the structures were fully characterized. In addition, transformation and equilibration between the alcohol iminiums (1-3) and the aza acetals 1a-3a were investigated by measurements of the NMR spectra in protic and aprotic deuteriumsolvents including alkali pyridine-d5, along with evaporation under reduced pressure and gradual additions of TFA, AcOH, and HCl. The results demonstrated that the transformation and equilibration were solvent-, base-, and acid-dependent. Especially, in aqueous biological fluid, these C20-diterpenoid alkaloids would more likely exist as the alcohol iminiums accompanied by anion counterparts in biosystems to increase their solubility, bioavailability, transportations, and functions. The absolute configurations of 1-3 were confirmed by X-ray crystallographic analysis of 2a.
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Received: 03 May 2016
Published: 27 May 2016
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| Fund:Financial support from the National Natural Science Foundation of China (NNSFC; Nos. 21132009, 30825044) and the National Science and Technology Project of China (Nos. 2012ZX09301002-002, 2011ZX0 9307-002-01) is acknowledged. |
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Corresponding Authors:
Jian-Gong Shi
E-mail: shijg@imm.ac.cn
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