Photo-induced intramolecular arene-olefin meta-cycloaddition of 5-phenyl-fluorinated-pent-1-enes

doi:10.1016/S0022-1139(99)00042-1

Journal of Fluorine Chemistry

Volume 97, Issues 1–2, 20 July 1999, Pages 149-156

https://doi.org/10.1016/S0022-1139(99)00042-1 Get rights and content

Abstract

A series of fluorinated angular and linear triquinanes and their aza-analogues have been synthesized by photo-induced intramolecular meta-cycloaddition of 5-phenyl-fluorinated-pent-1-enes.

Introduction

The meta- or 1,3-photoaddition of olefins to arenes is unique among the cycloaddition reactions. From the readily available materials under mild conditions, it provides a cycloadduct having three new rings and up to six stereocenters which can hardly be prepared by usual methods [1]. There are a variety of excellent examples of the synthetic use of the intramolecular meta-cycloaddition, but the synthetic potential of the reaction has by no means been fully exploited 2, 3. Thus, the intramolecular meta-cycloaddition of 5-phenylpent-1-ene derivatives has been recently used elegantly as the key step in the synthesis towards polyquinanes and fenestranes 4, 5. The former is the general skeleton for numerous natural products and the latter of theoretical importance with potential for use in materials and medicinal research 6, 7. In connection with the special character of fluorine atom, the introduction of fluorine into this intramolecular meta-cycloaddition would be of interest. However, to the best of our knowledge, no attempt has been made to introduce fluorine into the side chain of 5-phenylpent-1-ene system although several examples of fluorine atom or trifluoromethyl group fixed on the different position of the phenyl ring giving the normal photo adducts have been reported 8, 9. Herein, we present the results on the photochemistry of 5-phenyl-fluorinated-pent-1-ene and its aza-analogues.

Section snippets

Results and discussion

The vinyl bromide 1 was prepared by aldol condensation of o-anisaldehyde and acetone followed by saturation of the double bond with bromine and dehydrobromination with Et₃N. Two isomers 1a and 1b were obtained but not separated by usual flash chromatography. In connection with our previous finding that some inexpensive trifluoromethylating agents, such as FSO₂CF₂CO₂Me, FO₂SCF₂CF₂OCF₂CO₂Me and XCF₂CO₂Me (X=Cl, Br, I) can successfully replace halogen in vinyl, allyl, aryl and alkyl halides. Here,

Experimental

IR spectra were taken on Schimadzu-440 and Perkin-Elmer 983 spectrometers. $^{1} H NMR$ spectra were recorded on Varian EM-360A (60 MHz), FX-90Q (90 MHz) and Bruker AM 300 (300 MHz) NMR spectrometers. $^{19} F NMR$ spectra were recorded on a Varian EM-360L (56.4 MHz) NMR spectrometer. Chemical shifts were reported in parts per million relative to TMS as an internal standard for $^{1} H NMR$ and to CF₃COOH as an external standard for $^{19} F NMR$ . The solvent for NMR measurement was CDCl₃. MS and HRMS spectra were

Acknowledgements

We would like to thank Prof. Cong Zhang for his helpful discussion and the Chinese National Natural Science Foundation for the financial support.

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Photo-induced intramolecular arene-olefin meta-cycloaddition of 5-phenyl-fluorinated-pent-1-enes

Abstract

Introduction

Section snippets

Results and discussion

Experimental

Acknowledgements

Tetrahedron Lett.

Tetrahedron

J. Photochem. Photobiol., A; Chem.

J. Photochem. Photobiol., A; Chem.

J. Fluorine Chem.

J. Am. Chem. Soc.

Chem. Rev.

Chem. Rev.