129855-24-9Relevant academic research and scientific papers
Divergent reactivity of alkyl aryl sulfones with bases: Selective functionalization of ortho-aryl and α-alkyl units enabled by a unique carbanion transmetalation
Rehova, Lucie,Cisarova, Ivana,Jahn, Ullrich
supporting information, p. 1461 - 1476 (2014/03/21)
The electron-accepting sulfonyl group exhibits a strong acidifying influence on neighboring α-H atoms. The Julia and related olefinations are based on this effect. Here a surprising reversal in the metalation selectivity of branched alkyl aryl sulfones is described. Such sulfones were found to initially undergo directed ortho-metalation with good regioselectivity, despite having a more acidic α-H atom. The structure of the alkyl unit profoundly, but predictably, influences the regioselectivity of the attack of the base. In β- and γ-branched ortho-(alkylsulfonyl)aryllithiums a transmetalation to the α-carbanion proceeds only upon warming. Correspondingly generated ortho- or α-carbanions were then selectively applied thus permitting access to synthetically interesting compound classes. An unusual lithiation selectivity and subsequent transfer of the metal upon warming was observed for various branched alkyl phenyl sulfones. This divergent reactivity was used to prepare substituted aryl sulfones as well as olefins by application of the Julia reaction. Copyright
Divergent Reactivity of Alkyl Aryl Sulfones with Bases: Selective Functionalization of ortho-Aryl and α-Alkyl Units Enabled by a Unique Carbanion Transmetalation
?ehová, Lucie,Císa?ová, Ivana,Jahn, Ullrich
supporting information, p. 1461 - 1476 (2015/10/05)
The electron-accepting sulfonyl group exhibits a strong acidifying influence on neighboring α-H atoms. The Julia and related olefinations are based on this effect. Here a surprising reversal in the metalation selectivity of branched alkyl aryl sulfones is described. Such sulfones were found to initially undergo directed ortho-metalation with good regioselectivity, despite having a more acidic α-H atom. The structure of the alkyl unit profoundly, but predictably, influences the regioselectivity of the attack of the base. In β- and γ-branched ortho-(alkylsulfonyl)aryllithiums a transmetalation to the α-carbanion proceeds only upon warming. Correspondingly generated ortho- or α-carbanions were then selectively applied thus permitting access to synthetically interesting compound classes.
Tin-free radical-mediated C-C-bond formations with alkyl allyl sulfones as radical precursors
Kim, Sunggak,Lim, Chae Jo
, p. 3265 - 3267 (2007/10/03)
Primary alkyl radicals are generated highly efficiently and reliably from alkyl allyl sulfone precursors. The latter are effective in tin-free radical C-C-bond formations, including cyanation, vinylation, and allylation (see scheme; V-40 = 1,1′-azobis(cyc
Use of 2,3-Bis(phenylsulfonyl)-1-propene as a Multicoupling Reagent
Padwa, Albert,Kline, Donald N.,Murphree, S. Shaun,Yeske, Philip E.
, p. 298 - 306 (2007/10/02)
2,3-Bis(phenylsulfonyl)-1-propene (1) reacts with various amines to afford products derived from addition across the double bond as well as SN2' displacement.When treated with 2-piperidinemethanol, bissulfone 1 gave the expected SN2'
Synthesis of vinylic and cyclic sulfones via a radical addition-elimination sequence
Padwa, Albert,Shaun Murphree,Yeske, Philip E.
, p. 2983 - 2986 (2007/10/02)
Radical attack on the double bond of 2,3-bis(phenylsulfonyl)-1-propene leads to an intermediate sulfonyl stabilized radical. This species readily fragments to produce a new vinyl sulfone which can undergo further radical cyclization to give a six ring sul
