jo9705935_si_001.pdf (719.96 kB)
Download file

Chemistry of Conversions of [o-[1-Halo-1-(p-tolylsulfonyl)alkyl]benzyl]trimethylsilanes to o-Quinodimethanes and Benzocyclobutenes

Download (719.96 kB)
journal contribution
posted on 17.03.1998, 00:00 by Brian D. Lenihan, Harold Shechter
Trimethyl[o-[bromo(p-tolylsulfonyl)methyl]benzyl]silane (10) is prepared from o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (9), n-BuLi, and bromine. Sulfone 9 eliminates trimethylsilyl bromide upon reaction with TBAF in acetonitrile to give the presumed intermediate, α-sulfonyl-o-quinodimethane 11, which (1) dimerizes to disulfone 12 and (2) is trapped by alkyl fumarates to yield (p-tolylsulfonyl)tetrahydronaphthalenes 17a,b and 18a,b, respectively. Sulfone 9 is converted by n-BuLi and alkyl halides to α-alkyl-α-bromosulfones 19af which react with TBAF to give α-sulfonylbenzocyclobutenes 21af and vinyl sulfones 23af, apparently upon ring closure and upon 1,5-sigmatropic rearrangements of hydrogen in α-sulfonyl-o-quinodimethane intermediates 20af and 22af. Further, sulfone 9, n-BuLi, and tert-butyl hypochlorite yield α-chlorosulfone 26 and α,α-dichlorosulfone 27. TBAF effects dechlorotrimethylsilation of 27 to chloro(p-tolylsulfonyl)cyclobutene 28 presumably upon formation and cyclization of o-quinodimethane 29. Silanes 10, 19af, and 27 are therefore practical synthons for o-quinodimethane intermediates 11, 20af and 22af, and 29 respectively.