14元海洋西松烷型二萜类化合物肉珊瑚氧化萜的异常跨环环化产物：环氧化物-酮重排的异常立体化学

Unusual transannular cyclization products of sarcophytoxide, a 14-membered marine cembranoid: anomalous stereochemistry of epoxide-ketone rearrangement.

作者信息

Nii Keiji, Tagami Keiko, Matsuoka Keisuke, Munakata Tatsuo, Ooi Takashi, Kusumi Takenori

机构信息

Institute of Health Biosciences, The University of Tokushima Graduate School, Japan.

出版信息

Org Lett. 2006 Jul 6;8(14):2957-60. doi: 10.1021/ol0608404.

DOI:10.1021/ol0608404

PMID:16805526

Abstract

[reaction: see text] Treatment of sarcophytoxide with trimethylsilyl trifluoromethanesulfonate afforded an aromatic ketone as an unusual cyclization product. The modified Mosher's method and X-ray analysis performed on the aromatic ketone revealed that it is a 4:1 mixture of 8(R)- and 8(S)-enantiomers. It also suggested that the precursor ketone has 8(R)-configuration, which is contradictory to that expected from the ordinary epoxide-ketone rearrangement.

摘要

[反应：见正文] 用三甲基甲硅烷基三氟甲磺酸酯处理肉珊瑚氧化物得到一种芳香酮，作为一种不寻常的环化产物。对该芳香酮进行的改良莫舍尔方法和X射线分析表明，它是8(R)-和8(S)-对映体的4:1混合物。这也表明前体酮具有8(R)-构型，这与普通环氧化物-酮重排预期的构型相矛盾。