Preparation of beta- and gamma-trialkylstannyl alcohols and thiols by ring opening of oxiranes, oxetanes, thiiranes, and thietanes with (trimethylstannyl)lithium

Reaction of Me3SnLi with monoalkyl- and monoaryl-substituted oxiranes, e.g. oxiranes I (R1 = Me, Ph; R2 = R3 = H), followed by hydrolysis, yielded regioisomerically pure HOCR1R2CHR3SnR43 (II; R1, R2, R3 = same; R4 = Me). Polysubstituted oxiranes reacted with a loss in regioselectivity. E.g., oxirane I (R1 = Ph, R2 = H, R3 = Me) reacted with R43SnLi (R4 = Me, Bu) to give II and R43SnCR1R2CHR3OH (R1, R2, R3, R4 = same for both). Oxetanes III (R5 = H, Me, Ph) reacted with Me3SnLi to give R5CH(OH)CH2CH2SnMe3. Reaction of Me3SnLi with thiiranes was complicated by desulfurization. E.g., reaction of thiabicycloheptane IV with Me3SnLi gave stannylated thiol V, cyclohexene, and (Me3Sn)2S. Allylation of an intermediate stannylated lithium alkoxide in these reactions was performed. Reaction of epoxides, e.g. I (R1 = Me, R2 = R3 = H), with Me3SnLi, followed by addn. of H2C:CHCH2Br, yielded H2C:CHCH2OCHMeCH2SnMe3.