Preparation of bicyclic herbicide precursors by intramolecular stork-danheiser kinetic alkylation reactions of methyl 1-(haloalkyl)-3-methoxy-5-oxocyclohex-3-ene-1-carboxylate derivatives

Andris J. Liepa, John S. Wilkie, David A. Winkler, Kevin N. Winzenberg

Research output: Contribution to journalArticleOther

2 Citations (Scopus)

Abstract

Reductive alkylation of methyl 3, 5-dimethoxybenzoate with the dibromoalkane and the bromochloroalkane derivatives (4a-d) and (4e-g) afforded, after acid hydrolysis, the corresponding methyl 1- (haloalkyl)-3-methoxy-5-oxocyclohex-3-ene-1-carboxylate derivatives (6a-g). Reaction of (6a-c) with lithium diisopropylamide afforded methyl 3-methoxy-5-oxobicyclo[4.2.0]oct-3-ene- 1-carboxylate (2a), methyl 5-methoxy-7-oxo-1, 2, 3, 4, 7, 7a-hexahydro-3aH-indene-3a-carboxylate (2b) and methyl 6-methoxy-8-oxo-1, 3, 4, 5, 8, 8a-hexahydronaphtha1ene-4a(2 H)- carboxylate (2c), respectively. Compounds (2b) and (2c) were also obtained from the reaction of (6f) and (6g) with lithium diisopropylamide. Compounds (2a) and (2b) were each obtained as a single bridgehead isomer, the relative stereochemistry of ring fusion of which was assigned as cis on the basis of semiempirical molecular orbital calculations. Compound (2c) was obtained as a mixture of cis-and trans-fused bridgehead isomers. The ester (2b) was converted into the herbicide methyl 5, 7-dioxo-6-[1-[(prop-2-enyloxy) imino] butyl]octahydro-3aH-indene-3a-carboxylate (3a). © 1992 ASEG.

Original languageEnglish
Pages (from-to)759-767
Number of pages9
JournalAustralian Journal of Chemistry
Volume45
Issue number4
DOIs
Publication statusPublished - 1992
Externally publishedYes

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