Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Bew, Sean, Hiatt-Gipson, Glyn D., Mills, Graham P. and Reeves, Claire (2016) Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate. Beilstein Journal of Organic Chemistry, 12. pp. 1081-1095. ISSN 1860-5397

[img]
Preview
PDF (Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate) - Published Version
Available under License Creative Commons Attribution.

Download (1MB) | Preview

Abstract

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate.

Item Type: Article
Additional Information: © 2016 Bew et al; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc)
Uncontrolled Keywords: exchange reaction,atmospheric chemistry exchange reaction,halide,isoprene nitrate,monoterpene
Faculty \ School: Faculty of Science > School of Chemistry
Faculty of Science > School of Environmental Sciences
Depositing User: Pure Connector
Date Deposited: 31 May 2016 09:01
Last Modified: 14 Nov 2020 00:52
URI: https://ueaeprints.uea.ac.uk/id/eprint/59138
DOI: 10.3762/bjoc.12.103

Actions (login required)

View Item View Item