The first "green" asymmetric organocatalytic reaction in a supercritical carbon dioxide medium was elaborated. Under the proposed conditions (100 bar, 35 °C), α-nitroalkenes enantioselectively accept diphenylphosphite in the presence of bifunctional organocatalysts bearing the tertiary amino group and the squaramide fragment to afford corresponding β-nitrophosphonates in high yields and with enantioselectivities of up to 94% ee. By varying the catalyst structure it is possible to synthesize both β-nitrophosphonate enantiomers under these conditions. A significant potential of the supercritical extraction for product isolation and catalyst recovery was demonstrated. † Electronic supplementary information (ESI) available. See
Dioxide. -(KUCHUROV, I. V.; NIGMATOV, A. G.; KRYUCHKOVA, E. V.; KOSTENKO, A. A.; KUCHERENKO, A. S.; ZLOTIN*, S. G.; Green Chem. 16 (2014) 3, 1521-1526, http://dx.
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