Synthesis of cyclohexadienylstannanes from cyclohexenones

DORN, V. B.; LOCKHART, M. T.; BADAJOZ, MERCEDES; CHOPA, ALICIA

Florianópolis-Brasil

Congreso; 8th Latin American Conference on Physical Organic Chemistry; 2005

Recently, we have described that the photochemically induced reaction of vinyl diethyl phosphate esters with triorganostannyl anions in liquid ammonia, proceeds cleanly via an SRN1 mechanism. Continuing our studies on the synthesis of vinyltrimethylstannanes now we report our firsts results about the synthesis of cyclohexadienyltrimethylstannanes by the photostimulated reaction of cyclohexadienyl diethyl phosphates with trimethyltin anion (1) in liquid ammonia as solvent. The starting phosphates 2 - 5 were synthesized from the corresponding cyclohexenones. Meanwhile the reaction between 2 and 1 was negative, recovering the starting substrate, compounds 3 to 5 reacted with 1, under photostimulation, rendering the desired stannane in fair to good yields. There is no reaction in the dark and the photostimulated reaction is inhibited by p-DNB.