Study of the acid-catalyzed isomerization of dihydroveatchine.
Study of the acid-catalyzed isomerization of dihydroveatchine.
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DOI：
10.1021/np9701440
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发表时间：
1997-07
影响因子：
5.1
通讯作者：
H. K. Desai;Y. Bai;S. Pelletier
中科院分区：
文献类型：
--
作者：
H. K. Desai;Y. Bai;S. Pelletier
一项酸催化双氢紫檀碱异构化的研究(5)分离出了一个主要的化合物，醛6。结构6是由它的光谱数据导出的。用NaBH4还原6得到化合物7，通过详细的NMR研究（包括1D， 2D和选择性INEPT实验）以及制备其单和双（对硝基苯甲酰）衍生物8和9对其进行了表征。根据氘标记法得到的异构化产物的光谱数据，报道了6的形成机理。有趣的是，烯丙醇garryfoline(1)和dihydroveatchinine(5)的酸催化异构化产物是不同的，并且似乎依赖于C（15）羟基的构型取向。明确的核磁共振化学位移分配5也被报道。
A study of the acid-catalyzed isomerization of dihydroveatchine (5) resulted in the isolation of a single major compound, the aldehyde 6. Structure 6 has been derived from its spectral data. Reduction of 6 with NaBH4 gave compound 7, which was characterized through detailed NMR studies including 1D, 2D, and selective INEPT experiments, as well as preparation of its mono- and bis(p-nitrobenzoyl) derivatives 8 and 9. A plausible mechanism for the formation of 6, derived from the spectral data of the isomerized product obtained by deuterium labeling, is reported. Interestingly, the acid-catalyzed isomerization products of the allylic alcohols garryfoline (1) and dihydroveatchine (5) are different and appear to be dependent on the configurational orientation of the C(15) hydroxyl group. Unambiguous NMR chemical shift assignments for 5 are also reported.