A joint experimental and ab initio study on the reactivity of several hydroxy selenides. Stereoselective synthesis of cis-disubstituted tetrahydrofurans via seleniranium ions

doi:10.1016/S0040-4020(01)00618-4

Tetrahedron

Volume 57, Issue 31, 30 July 2001, Pages 6815-6822

https://doi.org/10.1016/S0040-4020(01)00618-4 Get rights and content

Abstract

The reactivity of several hydroxy selenides bearing an ethereal chain with catalytic amounts of perchloric acid in dichloromethane was investigated. Results showed that the position of the oxygen atom with respect to the seleniranium ring was crucial in order to get a good yield of the cyclized product. The factors on which yields of the 5-endo cyclization of the seleniranium ions depend were analysed by ab initio (HF/3-21G^∗) studies. An explanation of the different coordinating ability, towards the positively charged selenium atom, of the allylic OMe and homoallylic OH-2 groups was given.

Graphic

Introduction

Structurally complex tetrahydrofuran units are often found in many natural products such as polyether antibiotics and a particularly challenging aspect is the stereocontrolled synthesis of the substituted tetrahydrofuran unit, especially those in which there is a cis relationship between substituents at the 2 and 5 positions.¹ During the last decade several authors have prepared in a synthetically useful manner substituted tetrahydrofurans via 5-endo-cyclization of intermediate seleniranium,2., 3., 4., 5., 6., 7., 8. thiiranium⁹ or iodonium ions.10., 11. In the last years our efforts have been devoted to the stereoselective synthesis of oxygenated heterocyclic rings from mixtures of hydroxy selenides or by treatment of the appropriate unsaturated alcohol with a source of the electrophilic seleno species PhSe⁺, such as PhSeCl.12., 13., 14., 15., 16., 17., 18. Both the methods lead to oxygenated heterocyclic rings via the intermediate seleniranium ion. Recently we studied the behaviour of the intermediate seleniranium ion having two hydroxyl groups and an aliphatic R chain (Fig. 1).¹⁷ We found that the 5-endo-tet¹⁹ cyclization occurs only at high acid concentration or when the primary hydroxy group is protected.

Section snippets

Results and discussion

In order to gain deeper information about the influence of the R group in the 5-endo-tet cyclization, we have analysed the reactivity of hydroxy selenides 6 bearing, as R group, an oxygenated aliphatic chain (RCH₂OPG; RCH₂CH₂OPG). These compounds were prepared as outlined in Scheme 1. Epoxidation of homoallylic alcohols 4 using tert-butyl-hydroperoxide and VO(acac)₂ gave the syn-epoxy-alcohols with good stereoselectivity (>93:7), the configuration of the major epoxide being assigned by

Conclusion

The low yield for the cyclization of 6a,b could be ascribed both to the coordination of the positively charged phenylselenyl moiety by the benzyloxy group in the seleniranium ions and to the presence of the oxygen atom (of the benzyloxy group) that hampers the development of a partial positive charge at C-5 and then the rupture of the C⋯Se bond. Both these factors make the activation energy of the ring closure process high. In the cyclization of 6c,d both the coordination and some electronic

Experimental

Anhydrous solvents were distilled as follows: Tetrahydrofuran and diethyl ether were distilled under nitrogen from sodium benzophenone immediately prior to use. Dichloromethane was distilled under nitrogen from calcium hydride and used immediately. ¹H and ¹³C NMR spectra were recorded on a Bruker AC-E series 250 MHz spectrometer. IR spectra were recorded on a Perkin–Elmer infrared spectrophotometer (model 1310) using KBr cells. Flash chromatography was carried out using Macherey–Nagel silica gel

Acknowledgements

Financial support from the University of Palermo (funds for selected research topics) and Italian MURST within the National Research Project, ‘Non-aromatic heterocycles in stereocontrolled processes’ is gratefully acknowledged.

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A joint experimental and ab initio study on the reactivity of several hydroxy selenides. Stereoselective synthesis of cis-disubstituted tetrahydrofurans via seleniranium ions

Abstract

Introduction

Section snippets

Results and discussion

Conclusion

Experimental

Acknowledgements

Tetrahedron: Asymmetry

Tetrahedron

Tetrahedron

Tetrahedron

Tetrahedron Lett.

Tetrahedron

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett

Tetrahedron Lett.

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Tetrahedron Lett.

J. Org. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Eur. J. Org. Chem.

J. Chem. Soc., Chem. Commun.