Cu-promoted oxidative trifluoromethylation of terminal alkynes with difluoromethylene phosphobetaine

Article abstract of DOI:10.1002/cjoc.201400427

Difluoromethylene phosphobetaine (Ph₃P⁺CF ₂CO₂^-, PDFA), a known difluorocarbene reagent, was found to be able to efficiently trifluoromethylate terminal alkynes in the presence of Cu(I) and potassium fluoride. The transformation proceeded smoothly to afford the corresponding trifluoromethylated acetylenes in moderate yields. A difluorocarbene precursor, difluoromethylene phosphobetaine (Ph ₃P⁺CF₂CO₂^-, PDFA) was found to be able to act as a trifluoromethylating reagent in the presence of fluoride. The oxidative trifluoromethylation of terminal alkynes with PDFA promoted by Cu(I) occurred smoothly to give the corresponding trifluoromethylated acetylenes in moderate yields. Copyright

Full text of DOI:10.1002/cjoc.201400427

Supporting information
Cu-promoted Oxidative Trifluoromethylation of Terminal Alkynes
with Difluoromethylene Phosphobetaine
Xiao-Yun Deng,a Jin-Hong Lin,a Jian Zheng a and Ji-Chang Xiao*,a
aKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences,345 Lingling Road, Shanghai 200032, China.
Tables of Contents
1H NMR, 19F NMR, and 13C NMR Spectra of the target compounds………………………..S2

n-C3H7
CF3
3b
1H NMR

CF3
3c
1H NMR

CF3
3d
1H NMR

n-C5H11
CF3
3e
1H NMR

n-C3H7
CF3
3f
1H NMR

EtO
CF3
3i
1H NMR

CF3
MeO
3j
1H NMR

Br
CF3
3k
1H NMR

O2N
CF3
3l
1H NMR

CF3
N
3m
1H NMR

S
CF3
O
3n
1H NMR

CF3
3o
1H NMR