107224-29-3Relevant academic research and scientific papers
Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates
Górski, Bartosz,Basiak, Dariusz,Grzesiński, ?ukasz,Barbasiewicz, Micha?
, p. 7660 - 7663 (2019/08/30)
The reduction of the carbonyl group in acylated trifluoroethyl alkanesulfonates follows the Felkin-Ahn selectivity, and the so-formed diastereomeric β-hydroxysulfonyl intermediates undergo syn- and anti-fragmentation, depending on the reaction conditions. In effect, isomeric E- and Z-alkenes are formed in a stereodivergent manner, which mimics the mechanistic manifold of the Peterson olefination.
Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
Górski, Bartosz,Basiak, Dariusz,Talko, Alicja,Basak, Tymoteusz,Mazurek, Tomasz,Barbasiewicz, Micha?
supporting information, p. 1774 - 1784 (2018/04/27)
Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compounds, and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcohols (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, respectively. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alcohol groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
The invention of radical reactions. Part XXVII. Modified Julia synthesis of olefins using radical deoxygenation
Barton, Derek H. R.,Tachdjian, Catherine
, p. 7109 - 7120 (2007/10/02)
Xanthate derivatives of β-hydroxy sulfones react with methyl radicals generated from the photolysis of N-acetyloxy-2-thiopyridone to give the corresponding olefin. Under identical conditions a secondary alcohol is transformed into its thiopyridyl derivative.
