Phenols as Starting Materials for the Synthesis of Arylstannanes via SRN1¹

Phenols are converted into aryl diethyl phosphate esters (ArDEP), which on reaction with sodium trimethylstannide ( 1 ) or sodium triphenylstannide ( 2 ) in liquid ammonia afford arylstannanes by the S RN 1 mechanism. Thus, the photostimulated reaction of phenylDEP ( 3 ), (4-methoxyphenyl)DEP ( 4 ), (4-biphenyl)DEP ( 5 ), (1-naphthyl)DEP ( 6 ), (2-naphthyl)DEP ( 7 ), and 2- ( 34 ), 3- ( 32 ), and (4-pyridyl)DEP ( 35 ) with 1 leads to monostannylated product in fair to excellent yields (20−98%). Also, substrates containing two or three leaving groups react with 1 under irradiation, affording the corresponding di- or tristannylated aryl compounds. With tetraethyl m -phenylene bisphosphate ( 15 ), tetraethyl p -phenylene bisphosphate ( 21 ), (4-chlorophenyl)DEP ( 22 ), and 1,3,5-tris(diethylphospho)benzene ( 30 ), the di- or trisubstitution products 1,3-bis(trimethylstannyl)benzene ( 19 ) (79%), 1,4-bis(trimethylstannyl)benzene ( 23 ) (95 and 97%), and 1,3,5-tris(trimethylstannyl)benzene ( 31 ) (57%) are obtained, respectively. Also, the reaction of 6 and 7 with 2 leads to substitution products in quantitative yields, and the reaction of 21, 22, and (4-bromophenyl)DEP ( 24 ) with 2 affords 1,4-bis(triphenylstannyl)benzene ( 38 ) in high yields (70−100%). On the other hand, the results obtained in the photostimulated reaction of 24 and (4-iodophenyl)DEP ( 25 ) with 1, as well as in the reaction of 25 with 2, clearly indicate a fast HME reaction.