1-(Phenylsulfonyl)-2-(trimethylsilyl)ethane: A Valuable Intermediate for Synthesis of Olefins, Allyltrimethylsilanes, β-Trimethylsilyl Ketones, Vinyl Sulfones, 2-(Phenylsulfonyl)allyl Alcohols, and Varied Trimethylsilyl Derivatives

Article abstract of DOI:10.1021/jo00247a006

1-(Phenylsulfonyl)-2-(trimethylsilyl)ethane (1), prepared from 1-(trimethylsilyl)-2-(thiophenoxy)ethane and hydrogen peroxide, is converted by n-butyllithium to 1-(phenylsulfonyl)-1-lithio-2-(trimethylsilyl)ethane (2).Primary halides effect alkylation of 2 to 2-(phenylsulfonyl)-1-(trimethylsilyl)alkanes (3), reactions of which with n-butyllithium and then primary halides give higher 2-(phenylsulfonyl)-1-(trimethylsilyl)alkanes (5).Debenzenesulfonyltrimethylsilylation of 3 and 5 occurs efficiently with tetra-n-butylammonium fluoride (6) to yield mono- and disubstituted terminal olefins (7 and 8, respectively). 2-(Phenylsulfonyl)-3-(trimethylsilyl)-1-alkanols (14) result from reactions of 2 with aldehydes and ketones and then acidification.Allyltrimethylsilanes (18) are obtained by reductive elimination of mesylates (17) of 14 with sodium amalgam in methanolic disodium hydrogen phosphate. 2-(Phenylsulfonyl)-3-(trimethylsilyl)-1-propene (23), a 1-cationic-2-anionic equivalent (33), is preparable by (1) condensation of 1 and formaldehyde to 2-(phenylsulfonyl)-3-(trimethylsilyl)-1-propanol (24), (2) conversion of 24 by triphenylphosphine/carbon tetrachloride to 1-chloro-2-(phenylsulfonyl)-3-(trimethylsilyl)propane (25), and (3) elimination of 25 with triethylamine. β-Trimethylsilyl ketones (35) are produced by sodium amalgam reduction of α-phenylsulfonyl β-trimethylsilyl ketones (34) obtained by oxidation of 2-(phenylsulfonyl)-3-(trimethylsilyl)-1-propanols (14, R² = H) with chromic acid sulfonic acid in acetone.Acidification of the adducts from 2 and epoxides yields 3-(phenylsulfonyl)-4-(trimethylsilyl)-1-butanols (38).Primary and secondary alcohols 38 are converted by chromic acid/sulfuric acid to 3-phenyl sulfonyl 4-trimethylsilyl aldehydes and ketones (39). n-Butyllithium effects cyclization of methanesulfonates (40) of 37 to 1-(phenylsulfonyl)-1-<(trimethylsilyl)-methyl>cyclopropanes (42) with displacement of lithium methanesulfonate. 1-(Phenylsulfonyl)-2-n-hexyl-1-<(trimethylsilyl)methyl>cyclopropane (46a) and 1-(phenylsulfonyl)-2-phenyl-1-<(trimethylsilyl)methyl>cyclopropane (46b) are eliminated by 6 to 1-n-hexyl-2-methylenecyclopropane (47a) and 1-methylene-2-phenylcyclopropane (47b), respectively. 2-(Phenylsulfonyl)-1-alkenes (49) are prepared by reactions of 6 with 2-(phenylsulfonyl)-2-chloro-1-(trimethylsilyl)alkanes (48) obtained (1) from tert-butyl hypochlorite and 2-(phenylsulfonyl)-2-lithio-1-(trimethylsilyl)alkanes(4) and/or (2) by reaction of 1-(phenylsulfonyl)-1-chloro-2-(trimethylsilyl)ethane (50) with n-butyllithium and alkylations of the resulting 1-(phenylsulfonyl)-1-chloro-1-lithio-2-(trimethylsilyl)ethane (51).Synthesis of 50 is best effected by base-catalyzed cleavage of 3-(phenylsulfonyl)-3-chloro-4-(trimethylsilyl)-2-butanone (54) prepared from 1-acetyl-1-phenylsulfonyl)-2-(trimethylsilyl)ethane (53) and ...