Water promoted 9-fluorenylmethyloxycarbonyl detachment from amino acids in charged microdroplets.

Aqueous microdroplets exhibit unique properties and can trigger reactions that do not occur in bulk solution. Herein, we have demonstrated that water, in microdroplets, can reduce the energy barrier for the lone H transfer of 9-fluorenylmethyloxycarbonyl and promote its detachment from the amino group. This strategy works on various amino acids and opens opportunities of aqueous microdroplets in triggering organic reactions.

The Synthesis of Phosphonate Ester Containing Fluorinated Vinyl Ethers.

Three novel perfluorovinyl ethers containing phosphonate ester groups, diethyl 1,1,2,2,3,3,5,6,6-nonafluoro-4-oxa-5-hexenylphosphonate, (EtO)(2)P(O)(CF(2))(3)OCF=CF(2) (1), diethyl 1,1,2,2,4,5,5-heptafluoro-3-oxa-4-pentenylphosphonate, (EtO)(2)P(O)(CF(2))(2)OCF=CF(2) (2), and diethyl 1,1,2,2,4,5,5,7,8,8-decafluoro-4-trifluoromethyl-3,6-dioxa-7-octenylphosphonate, CF(2)=CFOCF(2)CF(CF(3))O(CF(2))(2)P(O)(OEt)(2) (3), have been synthesized. Perfluorovinyl ethers 1 and 2 were synthesized from methyl 4-trifluoroethenoxy-2,2,3,3,4,4-hexafluorobutanoate and methyl 3-trifluoroethenoxy-2,2,3,3-tetrafluoropropanoate, respectively, while perfluorovinyl ether 3 was synthesized either from 5-trifluoroethenoxy-4-trifluoromethyl-3-oxa-1,1,2,2,4,5,5-heptafluoropentylsulfonyl fluoride or methyl 6-trifluoroethenoxy-5-trifluoromethyl-4-oxa-2,2,3,3,5,6,6-heptafluorohexanoate. The carboxylate esters were converted to the corresponding fluoroalkyl iodides via a free-radical iododecarboxylation.