1,4-Dicyanobenzene → 4-(1-Aminocyclopropyl)benzonitrile

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Reaction Steps

To a solution of 1,4-dicyanobenzene (3.30 g, 25.8 mmol) in dichloromethane was added titanium(IV) isopropoxide (7.56 mL, 25.8 mmol) followed by ethylmagnesium bromide (3M in ether, 15.5 mL, 46.4 mmol) dropwise (exothermic, gas evolution after one eq of reagent added) and the mixture was stirred at r.t. for 45 min. Borontrifluoride diethyl etherate (5.71 mL, 46.4 mmol) was added and the mixture was stirred at r.t. for 2 h, quenched with NH4Cl and HCl and separated. The aqueous phase was washed once with ether and then the pH was adjusted to 9-10 with 10N NaOH (precipitate formation). The mixture was filtered through celite and the cake washed with water/EtOAc. The phases were separated and the aqueous phase extracted with EtOAc. The organic layers were combined, washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give the desired product as a viscous oil which solidified at −20° C. The crude was used directly without further purification.

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