ao7b00230_si_001.pdf (20.74 MB)
Basic Phosphonium Ionic Liquids as Wittig Reagents
journal contribution
posted on 2017-06-22, 08:13 authored by Dzmitry
S. Firaha, Anna V. Gibalova, Oldamur HollóczkiThe possibility of designing a solvent/reagent
for Wittig reactions
from basic phosphonium salts is explored theoretically. In the suggested
R4P+PhO– and Ph3PR+PhO– ionic liquids (ILs), the phenolate
anion is prone to remove the α-proton from the alkyl chains,
forming a phosphorous ylide. Significant hydrogen bonding between
the oxygen atoms of the anions and α-hydrogen atoms of the cations
were found by molecular dynamics simulations of these substances;
therefore, proton transfer between the two ions is inherently supported
by the structure of the liquid as well. The subsequent steps of the
Wittig reaction from the phosphorous ylide were also found to be energetically
possible. The mesoscopic structure of these materials exhibits a significant
segregation into polar and nonpolar domains, which may also allow
an easy dissolution of the substrates. The formation of a pentacoordinated
phosphorous derivative through P–O bond formation was found
to be also possible in the gas phase for both kind of compounds. Accordingly,
having such basic anions in phosphonium-based ILs may produce such
a neutral and therefore volatile species, which may hold further significant
applications for these solvents in ion-exchange and separation techniques
and in synthesis.
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Keywords
oxygen atomsmaterials exhibitsWittig Reagentsmesoscopic structureylidephosphonium-based ILsformationgas phaseWittig reactionsWittig reactionSignificant hydrogenBasic Phosphoniumphenolate anionα- protonPhOseparation techniquesproton transferalkyl chainsphosphonium saltsα- hydrogen atomsnonpolar domainsPh 3 PRdynamics simulationsR 4 P
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