Issue 9, 2002

Deoxygenation of tertiary and secondary alcohols ROH by thiol-catalysed radical-chain redox decomposition of derivatives ROCH2X to give RH and XCHO

Abstract

Compounds of the type ROCH2X, in which the substituent X is an electron-donating alkoxy, aryl or amido group, undergo thiol-catalysed radical-chain decomposition to give RH and XCHO. This reaction has been applied for the deoxygenation of representative tertiary and secondary alcohols ROH under metal-free conditions that require no stoichiometric co-reactant. Of the derivatives investigated, methoxymethyl (MOM) ethers and 1-alkoxymethylpyrrolidin-2-ones (PYRM ethers) proved to be the most generally successful and typical conditions for the redox decomposition to give RH involve heating under reflux in octane solvent in the presence of a peroxide initiator and tri-tert-butoxysilanethiol [(ButO)3SiSH] as a protic polarity-reversal catalyst. Conversions to RH were negligible in the absence of thiol. Several different types of tertiary alcohol, including steroidal and carbohydrate examples, were deoxygenated as their MOM and PYRM ethers to give very good isolated yields of RH. Although the MOM and PYRM ethers derived from many types of secondary alcohol also afforded good yields of RH, the MOM ether of diacetone D-glucose gave the 3-deoxy sugar in poor yield and the yield from the corresponding PYRM ether was still only moderate.

Graphical abstract: Deoxygenation of tertiary and secondary alcohols ROH by thiol-catalysed radical-chain redox decomposition of derivatives ROCH2X to give RH and XCHO

Article information

Article type
Paper
Submitted
07 Mar 2002
Accepted
20 Mar 2002
First published
10 Apr 2002

J. Chem. Soc., Perkin Trans. 1, 2002, 1161-1170

Deoxygenation of tertiary and secondary alcohols ROH by thiol-catalysed radical-chain redox decomposition of derivatives ROCH2X to give RH and XCHO

H. Dang and B. P. Roberts, J. Chem. Soc., Perkin Trans. 1, 2002, 1161 DOI: 10.1039/B202411J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements