1-(Phenylsulfonyl)-2-(trimethylsilyl)ethane. A valuable intermediate for synthesis of olefins, allyltrimethylsilanes, .beta.-trimethylsilyl ketones, vinyl sulfones, 2-(phenylsulfonyl)allyl alcohols, and varied trimethylsilyl derivatives

Abstract

225ChemInform Abstract The title compound (I) is converted by n-butyllithium (II) into its 1-lithio derivative (III) which is alkylated to yield the substituted alkanes (V). Repetition of this procedure gives the dialkylated products (VII). Elimination reaction of (V) and (VII) with tetrabutylammonium fluoride produces the corresponding terminal olefins (VIII). The allyltrimethylsilanes (X) are prepared from (III) and the carbonyl compounds (IX) by a method described earlier. Reductive debenzenesulfonylation of (XII), obtained from (III) and the aldehydes (XI), results in the formation of the β-trimethylsilyl ketones (XIII). Reaction of (III) with the epoxides (XIV) gives intermediate adducts which are converted via mesylates to the cyclopropanes (XV). Further reactions with (III) or (V) are described in the original paper.

The Julia Reaction

“…For example, primary and secondary a-metalated sulfones add smoothly to formaldehyde [16,17] (Scheme 3.7). Although this approach is quite successful, few examples have hitherto been reported [16][17][18][19][20][21][22][23].…”

Organic oxidations promoted in vortex driven thin films under continuous flow

“…aryl sulfones by reaction with hypochlorous acid, 47 but we note that, to the best of our knowledge, this is the first reported route to 6 using chlorine bleach. Furthermore, other reports of α-chlorination of allyl aryl sulfones relied on phase-transfer catalysis and the toxic hexachloroethane as the electrophilic chlorine source.…”

The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

“…Such sulfones have been prepared by oxidation of the corresponding sulfides 40,41 or by reaction of 2-(trimethylsi-lyl)ethanesulfinate with alkyl halides. 42 For preparing new unsaturated sulfones 53 and 54, Palmer and Fuchs have developed Wittig-type chemistry through reaction of aldehydes or ketones with the phosphonium salt 51 derived from chloromethyl 2-(trimethylsilyl)ethyl sulfide (Scheme 18).…”

“…In this work, Kocieñski prepared phenyl 1-substituted-2-(trimethylsilyl)ethyl sulfone intermediates such as 63 by reaction of iodotrimethylsilane with the lithium derivative of the corresponding non-silyl sulfones for example the sulfone 62 (Scheme 20). This sulfone was cleaved to obtain the diene 64 in good yield.This approach was developed and applied to the synthesis of many interesting 1-substituted and 1,1-disubstituted ethenes 67 and 69 (Scheme 21) 40,[43][44][45][46][47][48][49]. These compounds were obtained by treating with fluoride ions at 0-65°C the corresponding phenyl 1-substituted-2-(trimethylsilyl) ethyl sulfones 66 and/or 68 prepared readily from the lithium derivative 65 by the reaction of phenyl 2-(trimethylsilyl)ethyl sulfone and electrophiles.…”