1026751-54-1Relevant academic research and scientific papers
Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations
Dong, Xichang,Roeckl, Johannes L.,Waldvogel, Siegfried R.,Morandi, Bill
, (2021)
Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated using 1,2-dibromoethane, as well as 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, to dibrominate or dichlorinate, respectively, a wide range of alkenes in a simple setup with inexpensive graphite electrodes. Conversely, the hexachlorinated persistent pollutant lindane could be fully dechlorinated to benzene in soil samples using simple alkene acceptors.
Diastereoselective acyclic aza-[2,3] Wittig sigmatropic rearrangements
Anderson, James C.,Smith, Stephen C.,Swarbrick, Martin E.
, p. 1517 - 1521 (2007/10/03)
The scope of anion-stabilising groups in promoting and controlling the diastereoselection of the aza-[2,3] Wittig sigmatropic rearrangement has been assessed by the syntheses of allylic amines 1c-g that have incorporated SiPhMe2, Ph, SPh, SOPh and SO2Ph respectively at the C-2 position. The subsequent anionic [2,3]-sigmatropic rearrangements are analysed with respect to the extent of diastereoselection of the product homoallylic amines 2 and 3. It appears that silicon not only is the most efficient at electronically facilitating this rearrangement, but its steric bulk controls the diastereoselectivity of the process exclusively. Phenyl and phenylthio substituents also have a similar, but decreased, effect on diastereoselection that mirrors their lower steric bulk in comparison to the silicon derivative. Sulfoxide and sulfone substituents are incompatible with the reaction conditions required for rearrangement.
