Chloroiodomethane → HCID 19595652, compound

Participants

Reaction Conditions

Reaction Steps

In a 15 mL round-bottom flask (oven dried and under argon) was added anhydrous dichloroethane (6 mL) and diethyl zinc (0.34 mL, 3.3 mmol). The mixture was cooled to 0° C. and chloroiodomethane (0.43 mL, 6.0 mmol) was slowly added via syringe. The reaction mixture was stirred at 0° C. for 5 min. and a solution of the above homoallylic alcohol (2: R2 =H; 0.41 g, 1.57 mmol) in dichloroethane (2 mL) was slowly added. The mixture was allowed to warm to room temperature and stirred for one hour. The reaction mixture was then quenched with saturated NH4Cl and the aqueous phase was extracted with EtOAc (2×15 mL). The organic solution was washed with saturated NaCl, dried (Na2SO4) and concentrated in vacuo. Crude [1-(5,5,8,8-tetramethyl-3-propyloxy-5,6,7,8-tetrahydronaphthalen-2-yl)-cyclopropyl]ethanol (3: R2 =H) was recovered in 63% yield (0.27 g) and carried directly on to the next step. To a solution of the above cyclopropyl alcohol (3: R2 =H; 0.25 g, 0.92 mmol) in 5 mL CH2Cl2 at room temperature was added PCC (0.4 g, 1.84 mmol). The reaction mixture was stirred for 3 hours and then filtered and rinsed with 15% EtOAc/hexane through a pad of celite/silica gel. Solvent was removed in vacuo to provide 230 mg of 1-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-cyclopropaneacetaldehyde (4: R2 =H) as a white solid in 93% yield. 1H NMR (400 MHz, CDCl3) δ9.78 (t, J=2.5 Hz, 1H, aldehyde), 7.20 (d, J=8.1 Hz, 1H, aromatic), 7.18 (d, J=2.0 Hz, 1H, aromatic), 6.99 (dd, J=8.1 and 2.1 Hz, 1H, aromatic), 2.57 (d, J=2.6 Hz, 2H, CH2), 1.66 (s, 4H, 2CH2), 1.26 (s, 6H, 2CH3), 1.25 (s, 6H, 2CH3), 1.02 (dd, J=6.4, 4.7 Hz, 2H, CH2), 0.87 (dd, J=6.1,4.6 Hz, 2H, CH2).

Provenance & Evidence