The Biomimetic Synthesis and Final Structure Determination of (+)- and (−)-Centrolobine, Naturally Occurring Diarylheptanoid 2,6-cis-Disubstituted Tetrahydro-2H-pyrans
The Biomimetic Synthesis and Final Structure Determination of (+)- and (−)-Centrolobine, Naturally Occurring Diarylheptanoid 2,6-cis-Disubstituted Tetrahydro-2H-pyrans
复制标题
(+)- 和 (−)-Centrolobine（天然存在的二芳基庚烷 2,6-顺式二取代四氢-2H-吡喃）的仿生合成和最终结构测定
DOI：
--
复制
发表时间：
2010
期刊：
影响因子：
--
通讯作者：
P. Rüedi
中科院分区：
文献类型：
--
作者：
Frank Rogano;P. Rüedi
通过氧化环化反应合成了对映体纯的标题化合物。该方法被认为是一个仿生苯酚氧化通过中间体醌甲基化物。前体的绝对构型得以保留，过渡态采用空间上最有利的2，6-取代基的双赤道排列，得到顺式构型的天然产物。结果明确地建立了绝对构型和与手旋光数据的相关性。此外，还解决了以前没有讨论过的区域异构问题，确认了天然着丝粒中MeO基团位置的原始归属。因此，这些结果是我们在早期评论文章中假设的长期不一致的校正的实验证据。
The enantiomerically pure title compounds were prepared by oxidative cyclization of their optically active diarylheptanoid precursors. The approach is considered as a biomimetic phenol oxidation via an intermediate quinone methide. The absolute configuration of the precursors is retained, and the transition state adopts the sterically most favorable diequatorial arrangement of the 2,6-substituents to afford the cis-configured natural products. The outcome unambiguously establishes the absolute configurations and the correlation with the chiroptical data. In addition, a problem of regioisomerism that had not been discussed before was solved, and the original assignment of the position of the MeO group in the natural centrolobines could be confirmed. As such the results are the experimental evidence for the corrections of long-term inconsistencies we had postulated in an earlier review article.
登录
查看更多内容
影响因子：
5.2
作者：
Evans, PA;Cui, J;Gharpure, SJ
通讯作者：
Gharpure, SJ
通过铟介导的串联烯丙基化/Prins环化反应环境友好地合成顺式2,6-二取代四氢吡喃。
DOI：
10.1021/jo7016857
发表时间：
2008
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Pham,Minh;Allatabakhsh,Amir;Minehan,ThomasG
通讯作者：
Minehan,ThomasG
影响因子：
5.2
作者：
He A;Sutivisedsak N;Spilling CD
通讯作者：
Spilling CD
影响因子：
5.2
作者：
Marumoto, S;Jaber, JJ;Rychnovsky, SD
通讯作者：
Rychnovsky, SD
DOI：
10.1107/s0108767394005726
发表时间：
1995-01-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION A
影响因子：
--
作者：
BLESSING, RH
通讯作者：
BLESSING, RH