PDF《Supporting Information》

Supporting Information Value of Zeolites In Asymmetric Induction During Photocyclization of Pyridones, Cyclohexadienones and Naphthalenones Karthikeyan Sivasubramanian, Lakshmi S.

Kaanumalle, Sundararajan Uppili and V. Ramamurthy * Department of Chemistry, University of Miami, Coral Gables, Fl 33124, USA Contents Synthesis of reactants 1, 2,

4 and

6 pp. 2-12 Characterization of reactants 1, 2,

4 and

6 pp. 12-27 Characterization of photoproducts pp. 28-36 Analysis conditions of photoproducts pp. 37-43

2 Synthesis of 2,2-dimethyl-1,2-dihydro-naphthalenone (1a) Scheme S1: Synthesis of 2,2 dimethyl-1,2-dihydro-napthalenone Step 1: Synthesis of 2,2-dimethyl-α-tetralone (DMT): To a cold (0°C) suspension of KH in mineral oil 3g (75mmol) and methyl iodide 19g (134mmol) in dry (distilled) THF (200ml) under a dry atmosphere of nitrogen gas, was added α-tetralone 5g (34.2mmol) in THF (200ml) over 0.5hr. The solution was allowed to warm up to room temperature after the initial rapid evolution of hydrogen had ceased and was stirred for 32hrs. The reaction was then carefully quenched by adding aqueous ammonium chloride followed by extraction with diethyl ether (three 100ml portions). The organic layer was washed with water and brine and dried over magnesium sulfate and concentrated in vacuo. Fractional vacuum distillation yielded product as a straw colored liquid. (5.42g, 91%). Step 2: Synthesis of 2,2-dimethyl-1,2-dihydro-naphthalenone: A mixture of 1.51g (0.0087mol) of the preceding ketone, 1.96g (0.011mol) of N-bromosuccinimide, 5.8ml of carbon tetrachloride, and 0.02g of benzoyl peroxide was refluxed in an atmosphere of nitrogen for 12hrs. The cooled mixture was filtered to remove precipitated succininide and evaporated to remove solvent. The residue was refluxed with 15ml of 20% ethanolic potassium hydroxide for 12hrs and the solvent again evaporated. This residue was treated with water and extracted with ether. Fractional vacuum distillation yielded product as a colorless liquid. (0.9g, 60%).

3 Synthesis of 3,4-dihydro-3,3-dimethyl-4-oxonaphthalene-1-carboxylic acid Scheme S2: Synthesis of 2,2 dimethyl-1,2-dihydronaphthalenone-4-carboxylic acid. Synthesis of 2,2-dimethyl-1,2-dihydronapthalenone-4-carboxylic acid Step 1: Oxidation of dimethyltetralone to 2,2-dimethy-1,4- napthaquinone: In a

250 ml round bottom flask, 5.5g of dimethyltetralone, 50ml of dichloromethane and 9ml of water were taken. 20ml of t-butylhydroperoxide (t-BuOOH) and 0.3g of chromic oxide (CrO3) were added to this solution and the reaction mixture was stirred vigorously for

4 days. The hydroperoxide and the chromic oxide were replenished by adding 0.25g of CrO3 and 20ml of t-BuOOH. The reaction was quenched with dilute aqueous sodium thiosulphate solution filtered and passed through celite. The dione was extracted using ether, washed with water, brine and dried with anhydrous sodium sulfate. The solvent was evaporated and the dione was purified as a pale yellow solid using column chromatography (silica column, 30% dichloromethane in hexane). Step 2: Preparation of the vinyl triflate: To a cold (-78o C) solution of LDA (10.8mmol, formed from the reaction between diisopropylamine (1.7ml, 11.8mmol) and n-BuLi (10.8mmol) taken in a round bottomed flask under a dry atmosphere of nitrogen was added the above-prepared dione (1.85g, 9.84mmol) in THF (10ml) over

5 minutes.

4 The enolate was allowed to form in the cold for 1.5 hours. Solid N-Phenyl triflimide (4.04g, 11.3 mmol) was added in one portion. The suspension was allowed to warm to room temperature and was stirred for