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

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-hexahydronaphthalene4a(2H)-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-indence-3a-carboxylate (3a).