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Synthesis of ethyl 1-nitro-1,2,3,5,6,7,8,8a-octahydro-1-naphthalenecarboxylate via a Diels-Alder pathway
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Synthesis of ethyl 1-nitro-1,2,3,5,6,7,8,8a-octahydro-1-naphthalenecarboxylate via a Diels-Alder pathway

Panagiota Tsetsakos
Master of Science (M.S.), Drexel University
May 2014
DOI:
https://doi.org/10.17918/etd-4501
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Tsetsakos_Panagiota_20141.33 MBDownloadView

Abstract

Chemistry Organic compounds--Synthesis Diastereoisomers
Previously, ethyl 1-nitro-1,2,3,5,6,7,8,8a-octahydro-1- naphthalenecarboxylate was synthesized via tandem Mitsunobu cyclization - [3,3]-sigmatropic rearrangement of ethyl 5-(cyclohex-1-en-1-yl)-5-hydroxy-2- nitropentenoate. It was obtained in 48% yield as a 90:10 mixture of diastereomers by this route.1 In this study, ethyl 1-nitro-1,2,3,5,6,7,8,8aoctahydro- 1-naphthalenecarboxylate was obtained by an alternate reaction pathway. The Diels-Alder reaction of ethyl 2-nitro-2-propenoate generated in situ and 1-vinylcyclohexene afforded ethyl 1-nitro-1,2,3,5,6,7,8,8a-octahydro-1- naphthalenecarboxylate in 63% yield as a 70:30 mixture of diastereomers. The same major diastereomer predominated in both the Diels-Alder and tandem cyclization - rearrangement routes. The yield was higher but the stereoselectivity was lower for the Diels- Alder route. Attempts to separate the product diastereomers by chromatography were unsuccessful.

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