113405-31-5

Upstream product

• 6485-40-1 (R)-Carvone 
• 917-54-4 methyllithium 
• 106-95-6 allyl bromide 
• 24120-78-3 (1S,4R,6S)-1-methyl-4-(2-propenyl)bicyclo<4.1.0>heptan-2-one 
• 213833-70-6 (3R,5R)-(5-isopropenyl-2,3-dimethylcyclohex-1-enyloxy)trimethylsilane 
• 15681-48-8 dimethyllithium cuprate 

Downstream Products

• 214215-76-6 Acetic acid (1R,3R,4S)-3,4-dimethyl-5-oxo-4-(2-oxo-propyl)-cyclohexyl ester 
• 214215-78-8 (-)-(5R,6S)-5,6-dimethyl-6-(2-oxopropyl)cyclohex-2-enone 
• 39900-30-6 (-)-(2S,3R)-2,3-dimethyl-2-(2-oxopropyl)cyclohexanone 
• 175779-08-5 (2S,3R,5R)-5-isopropenyl-2,3-dimethyl-2-(2-oxopropyl)-cyclohexanone 

Relevant academic research and scientific papers

Chiral synthons from carvone. Part 50. Enantiospecific approaches to both enantiomers of bicyclo[4.3.0]nonane-3,8-dione derivatives

Enantiospecific synthesis of both enantiomeric forms of bicyclo[4.3.0]nonane-3,8-dione derivatives has been described starting from (R)-carvone employing two different cyclopentannulation methodologies. Thus, in the first methodology, carveol (5) was converted into tricyclic ketone 4 employing a Claisen rearrangement and intramolecular diazo ketone cyclopropanation reactions. Degradation of the isopropenyl group followed by cyclopropane cleavage and cuprate addition generated the dione (-)-12a. Whereas, a Wacker mediated cyclopentannulation of (R)-carvone via the dione 15 furnished the, enone 17. Functional group manipulation including the degradation of isopropenyl group transformed the enone 17 into the dione (+)-12a, which on regioselective ketalisation generated the ketoketal (+)-2.

Enantiospecific synthesis of (+)-(1S,2R,6S)-1,2- dimethylbicyclo[4.3.0]nonan-8-one and (-)-7-epibakkenolide-A

Synthesis of the chiral bicyclic ketone mentioned in the title starting from R-carvone, and its elaboration to 7-epibakkenolide-A is described. Conjugate addition of dimethyl copperlithium to R-carvone followed by alkylation of the intermediate enolate generated the allylated compound 6, which was transformed into the diketone 12 via a sequence of reactions comprising regiospecific Wacker oxidation, ozonation-Criegee rearrangement as key reactions. Intramolecular aldol condensation followed by catalytic hydrogenation converted the diketone 12 into the bicyclic ketone (+)-3, the optical antipode of the compound derived from the sesquiterpenes bakkenolide- A and fukinone. A 5-exo-dig radical cyclisation based strategy transformed the bicyclic ketone 3 into chiral 7-epibakkenolide-A.

Some novel electron transfer mediated cascade ring-opening reactions of bicyclo[4.1.0]ketones

The radical ring-opening reactions of cyclopropyl ketones, mediated by samarium (II) iodide and other electron transfer agents are described. This strategy allows tandem rearrangement cyclisation reactions and the trapping of the resultant samarium (III) enolates by a variety of electrophiles, for the construction of complex bicyclic systems.

Enantioselective synthesis of both (+)-and (-)-derivatives of bicyclo[4.3.0]nonan-8-one and -3,8-diones from R-carvone 1

Enantioselective synthesis of both the enantiomeric forms of the hydrindane derivatives mentioned in the title, potential chiral precursors in terpenoid synthesis, starting from R-carvone employing two different cyclopentannulation methodologies is described.