59034-54-7

Upstream product

• 93-58-3 benzoic acid methyl ester 
• 74-88-4 methyl iodide 
• 30889-20-4 methyl cyclohexa-2,5-diene-1-carboxylate 
• 67-56-1 methanol 
• 52457-01-9 3-Methylcyclohexa-1,4-diene-3-carboxylic acid 
• 59741-68-3 C₉H₁₂O₂ 

Downstream Products

• 113445-16-2 (E)-3-Isopropylamino-1-(1-methyl-cyclohexa-2,5-dienyl)-propenone 
• 699-42-3 1-methyl-2,4-cyclohexadienecarbonsaeure-methylester 
• 72469-77-3 (1-methylcyclohexa-2,5-dien-1-yl)methanol 
• 52457-01-9 3-Methylcyclohexa-1,4-diene-3-carboxylic acid 
• 177315-43-4 (2S,5R)-2-Benzyloxy-5-[(S)-hydroxy-(1-methyl-cyclohexa-2,5-dienyl)-methyl]-3,3-dimethyl-cyclopentanone 
• 177315-34-3 Acetic acid (S)-((1R,3S)-3-benzyloxy-4,4-dimethyl-2-oxo-cyclopentyl)-(1-methyl-cyclohexa-2,5-dienyl)-methyl ester 
• 152455-13-5 1-methyl-2,5-cyclohexadiene-1-carboxaldehyde 
• 62680-14-2 1-methyl-4-oxocyclohexa-2,5-dienecarboxylic acid methyl ester 

Relevant academic research and scientific papers

Diastereoselective alkylation reactions of 1-methylcyclohexa-2,5-diene-1- carboxylic acid

The deprotonation and alkylation of 1-methylcyclohexa-2,5-diene-1- carboxylic acid has been investigated under a range of conditions. In all cases, the formation of compounds 14 was found to be completely stereoselective, although compound 14c was formed as an impurity when alkyl iodides were used as electrophiles, and doubly-alkylated compounds 17 were formed in some cases when alkyl bromides were used.

Stereoselectivity control by oxaspiro rings during Diels-Alder cycloadditions to cross-conjugated cyclohexadienones: The syn oxygen phenomenon

The diastereofacial selectivity operating in Diels-Alder additions involving spirocyclic cross-conjugated cyclohexadienones with dienes of varying reactivity has been investigated. The study has included the ether series 1a-c as well as the lactone/ketone pair 2a/2b. In all cases, the preferred [4+2] cycloaddition pathway consisted of bonding from that π-surface syn to the oxygen atom. 4-Substituted-4-methyl-2,5-cyclohexadienones (monocyclic systems) were also examined and found to undergo bond formation preferentially from the face bearing the more electron-withdrawing of the two groups at the 4 position. Kinetic parameters were determined for the cycloaddition of 1a and 2a to cyclopentadiene. The rate acceleration profile of solvents was in the order CF3CH2OH ? CH3CN～CH2Cl 2 for the production of 9a from 1a and CF3CH2OH ? CH2Cl2 > CH3CN for the production of 21a from 2a, respectively. This spread in polarity had no major impact on product distribution, a phenomenon also reflected in the behavior of 4-substituted-4-methyl-2,5-cyclohexadienones under comparable conditions. Theoretical assessment of these experimental facts was undertaken at the HF/6-31G* level. The facial selectivity is understandable in terms of the secondary interaction between the HOMO of the diene and LUMO of the dienophile as well as the effective hyperconjugation between the newly forming bond and the 4-anti-C-C σ-orbital due to the more electron-donating bond, as defined by the Cieplak model.

A chemoenzymatic approach to the taxoid BC-substructure

The synthesis of a homochiral taxoid BC-unit containing the required functionalities on the B-ring periphery and a conveniently functionalized C-ring moiety by combination of enzymatic hydrolysis and the aldol-annelation-fragmentation sequence is describe

Studies towards the total synthesis of taxoids. A straightforward procedure for the taxoid BC substructure

The aldol condensation of the ketone 6 and the aldehyde 7 followed by an annelation-fragmentation afforded the bicyclo[6.4.0][dodecane derivative 3 with the appropriate functionalities for further elaboration.

CHEMOSELECTIVE INTRAMOLECULAR NITRONE-OLEFIN CYCLOADDITION : AN EFFICIENT ROUTE TO FUNCTIONALIZED CIS HYDRINDANE SYSTEMS

Isoxazolidines 5a-c and 8 were obtained via chemoselective nitrone-olefin cycloaddition in suitably modified 1,4-cyclohexadienes 1a-c; 5a and 5c were transformed to highly functionalized cis-hydrindanes.

Uncatalyzed Sigmatropic 1,5-Shift of Acyl Groups in the Thermolysis of 5-Acyl-5-methyl-1,3-cyclohexadienes

Four different 5-acyl-5-methyl-1,3-cyclohexadienes 1a-d (R=COOCH3, COCH3, COC6H5, CHO) have been shown to yield mixtures of 1,3-disubstituted cyclohexadienes 2-7 and 1,3-disubstituted aromatic product 8 upon thermolysis at 150-300 deg C in solution and at 350-500 deg C in the gas phase in a flow system.Two reaction pathways are considered for the rearrangement of the C-Skeleton.For the ester 1a 13C-isotopic substitution shows that products arise to 75-86percent through a 1,5-sigmatropic shift of the methoxycarbonyl group and to 14-25percent through a sequence of reaction steps involving a 1,7-H-shift reaction in an acyclic intermediate.For the more reactive compounds 1b-d isomerization is assumed to follow the 1,5-sigmatropic pathway exclusively.A kinetic study yields the following sequence for the migration tendency of acyl groups toward sigmatropic 1,5-shift: COOCH3 COCH3 COC6H5 CHO.