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2 hours. Workup with 5% aqueous sodium bicarbonate was followed by extraction into ether, water and brine washes, MgSO4 drying and solvent removal under vacuum. Flash chromatography (silica gel, 15% ether in petroleum ether) furnished the vinyl triflate as a viscous oil (75% pure by GC). Further purification was not attempted C this product was carried through to the next reaction. Step 3: Methoxy carbonylation of the vinyl triflate: To a solution of Pd(OAc)2 (176mg, 0.8mmol), triphenylphosphine (444mg, 1.7mmol), diisopropylethylamine (Huning'

s base, 4.5ml, 26mmol) and methanol (20mL) in dry DMF( 50ml) under a dry nitrogen atmosphere, was added the vinyl triflate isolated from the previous reaction. A stream of CO was bubbled through the solution for

9 hours. Standard workup with ether and water gave a black oil after the removal of solvent. Flash chromatography (silica gel, 12% ether in petroleum ether) gave the product as a pale yellow liquid (1.33g , 60% over two steps). Step 4: Hydrolysis of ester to acid: The ester obtained in the above step was stirred with 10% LiOH solution in methanol water mixture for 8-12 hours. Methanol was removed under vacuum and added cold water to this mixture and acidified with dilute hydrochloric acid to precipitate the acid. The acid was filtered, dried and subsequently used for the amidation step. Synthesis of chiral amides and esters of 2,2-dimethyl-1,2-dihydronapthalenone-4- carboxylic acid (Scheme S3) The above acid was stirred with

1 equivalent of chiral amine/alcohol along with

1 equivalent of EDC and catalytic amount of DMAP in dichloromethane to obtain the desired chiral amide or ester. In yet another route, the triflate obtained after the step III was stirred with atleast two equivalents of chiral alcohol or amine in the presence of

1 equivalent of DIPEA, catalytic amount of Pd(OAc)2-PPh3 in DMF(for esters) or dichloromethane (for amide) purged with carbon monoxide gas. A positive pressure of CO was maintained throughout the reaction. DIPEA was avoided during the synthesis of

5 amides as the free amines by themselves act as base. All the chiral compounds were purified by column chromatography (silica gel). A 25% ethylacetate in hexane mixture and 12% ethyl ether in hexane was used as eluent for amide and ester systems respectively. (A) EDC/DMAP/ amine or alcohol (B) Pd(OAc)2/PPh3/DIPEA/CO/alcohol (or) Pd(OAc)2/PPh3/CO/Amine Scheme S3: Synthesis of chiral amides and esters.

6 Synthesis of 3,3,5-Trimethyl-4-oxo-cyclohexa-1,5-diene carboxylic acid Scheme S4: Synthesis of 3,3,5-Trimethyl-4-oxo-cyclohexa-1,5diene carboxylic acid. Step

1 Synthesis of 2,6,6-trimethyl-cyclohexa-2,4-diene-1-one-4-triflate: In a clean dry 100ml

3 necked round-bottomed flask 20ml of LDA was taken at C78o C and stirred for

5 minutes under nitrogen. 5g of 4-oxoisophorone was dissolved in 20ml of dry THF and this solution was added in drops using a dropping funnel onto the cooled LDA over a period of

5 minutes. The enolate was allowed to form over a period of

2 hrs and 10.0g of solid N-phenyl triflimide was added in one portion to the above enolate and the suspension was stirred continuously and warmed to room temperature. Stirring was continued for additional 12hrs. The reaction mixture was quenched with saturated ammonium chloride solution and extracted with ether. The ether extract was washed thrice with water, 5% sodium bicarbonate solution and dried using anhydrous sodium sulfate. The solvent was removed under suction and the crude triflate was purified by column chromatography (silica gel, 15% ether in hexane). The triflate was obtained as a yellow liquid. (85% yield).