首次报道 Friedel-Crafts 环化反应得到（10-羟基-9,10-二氢蒽-9-基）磷翁盐，而没有预期的 Bradsher 脱水。

The First Example of the Friedel-Crafts Cyclization Leading to (10-Hydroxy-9,10-dihydroanthr-9-yl)phosphonium Salts without the Expected Bradsher Dehydration.

机构信息

Division of Organic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland.

Institute of Chemistry, Faculty of Science and Technology, Jan Długosz University in Częstochowa, Armii Krajowej 13/15, 42-201 Częstochowa, Poland.

出版信息

Int J Mol Sci. 2024 Feb 1;25(3):1741. doi: 10.3390/ijms25031741.

DOI:10.3390/ijms25031741

PMID:38339017

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10855353/

Abstract

The reaction of (acetalaryl)arylmethanols with various phosphines PRRR (R = R = R = Ph; R = R = Ph, R = Me and R = R = Me, R = Ph) under acidic conditions (e.g., HCl, HBF, TsOH) unexpectedly led to the formation of (10-hydroxy-9,10-dihydroanthr-9-yl)phosphonium salts instead of the corresponding anthryl phosphonium salts. The cyclization occurred according to the Friedel-Crafts mechanism but without the usually observed Bradsher dehydration, giving cyclic products in the form of isomers and their conformers. In case of electron-rich and less-hindered dimethylphenylphosphine, all four stereoisomers were recorded in P{H} NMR spectra, while for the other phosphines, only the two most stable / stereoisomers were detected. This study was supported by DFT and NCI calculations in combination with FT-IR analysis.

摘要

(缩醛芳基)芳基甲醇与各种膦 PRRR（R = R = R = Ph；R = R = Ph，R = Me 和 R = R = Me，R = Ph）在酸性条件下（例如 HCl、HBF、TsOH）的反应出乎意料地导致了（10-羟基-9,10-二氢蒽-9-基）磷翁盐的形成，而不是相应的蒽基磷翁盐。环化反应根据 Friedel-Crafts 机理发生，但没有通常观察到的 Bradisher 脱水，以异构体及其构象体的形式得到环状产物。在富电子和位阻较小的二甲基苯基膦的情况下，在 P{H}NMR 光谱中记录了所有四个立体异构体，而对于其他膦，则仅检测到两种最稳定的立体异构体。这项研究得到了 DFT 和 NCI 计算以及 FT-IR 分析的支持。