Discovery and Total Synthesis of Seco-acorane Sesquiterpenoids from Chloranthus holostegius: Determination of Absolute Configuration and Spontaneous Acetalization
Shihao Cheng, Jie Wen, Houli Jiang, Yuhang Zhou, Yi Zhu, Danyang Zhang, Lingyi Kong, Jun Luo
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引用次数: 0
Abstract
Shimianoids A–C, rare nor-acorane sesquiterpenoid
(1) and aromatic seco-acoranes (2/3) featuring an aldehyde group, along with
their spontaneous
acetalization products with methanol-d4 (2a/3a), were isolated and elucidated
from Chloranthus holostegius var. shimianensis. The undetermined absolute configurations
of the flexible side chain and intriguing spontaneous acetalization
of compounds 2/3 prompted our total synthesis
study. Ultimately, compounds 2/3 and their
acetalization products with methanol-d4 (2a/3a) and CH3OH (2b/3b) were synthesized via a redox-relay Heck reaction
of 4-tolylboronic acid with (±)-sulcatol, followed by oxidation
and acetalization. The absolute configurations of C7/10 at the flexible
side chain were determined by Mosher’s and ECD methods of the
synthetic intermediate, and the spontaneous reversible acetalization
was confirmed. Finally, a library of 26 aromatic seco-acorane sesquiterpenoids was constructed for bioactivity screening.
期刊介绍：
Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.
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