New
New Stable
Fluorinating Reagent
with Ease of Handling
(Hara Reagent)
IF5
.
. HF
N
[P2140]
Advantages
・Air-Stable and Non-Hygroscopic Crystalline
・Easy to Handle
・Widely Applicable to Various Fluorinations
of Sulfides
IF 5 -Pyridine-HF (P2140), which was first reported by Hara et al., is a novel fluorinating
reagent. Pentafluoroiodide (IF5) is a strong fluorination liquid agent, but it is unstable in air
and decomposes, generating HF. P2140 is a crystalline solid reagent with air stability and
non-hygroscopicity which makes it easier to handle, and can be used as an alternative
reagent to IF 5 . P2140 can be applied to various fluorination reactions of sulfides as
follows.1-4) In addition, P2140 iodofluorinates alkenes with streo- and regioselectivity.5)
Fluorination of the α-Positon of a Sulfide1)
Cl
P2140 (2.3 eq.)
S
CH3
Cl
CH2Cl2, rt, 24 h
CO2Et
S
CH3
Y. 89%
Cl
Ph
F
P2140 (1.5 eq.)
S
CO2Bu
CO2Et
F
CH2Cl2, rt, 24 h
Application Example (first reaction formula)
Ph
F
CO2Bu
Y. 89%
To a CH2Cl2 solution (2 mL) of ethyl 2-[(4-chlorophenyl)thio]propanoate (122 mg, 0.5 mmol)
is added P2140 (370 mg,1.15 mmol) at room temperature, and the mixture is stirred at room
temperature for 24 h. The resulting dark red solution is poured into water (20 mL) and
extracted with CH2Cl2 (20 mL x 3). The combined organic layer is washed with aq. NaHCO3
and aq. Na2S2O3, and dried over MgSO4. After concentration under reduced pressure, the
residue is purified with silica gel column chromatography (eluent: hexane/ether) to give ethyl
2-[(4-chlorophenyl)thio]-2-fluoropropanoate in 89% yield (117 mg).
1) S. Hara, M. Monoi, R. Umemura, C. Fuse, Tetrahedron 2012, 68, 10145.
New Stable Fluorinating Reagent with Ease of Handling (Hara Reagent)
Other Applications
Desulfurizing-Difluorination of Aldehyde and Ketone Dithioacetals1)
SPh
F
SPh
P2140 (2 eq.)
F
CH2Cl2, rt, 24 h
Y. 62%
Trifluoromethylation of Aldehyde Thioacetal Derivatives1)
S
S
SCH3
CF3
P2140 (3 eq.)
CH2Cl2, rt, 12 h
Y. 78%
Desulfurizing-Fluorination of Methylthiomethyl Ethers and Esters2)
OCH2F
OCH2SCH3 P2140 (1.1 eq.)
CH2Cl2, rt, 3.5 h
Ph
Y. 78%
Ph
Conversion of Dithiocarbonates to OCF2SCH3 or OCF33)
O CF2 SCH3
P2140 (1.1 eq.)
S
O C SCH3
i
CH2Cl2, rt, 3h
i
Y. 87%
Pr
P2140 (2 eq.)
Et3N-6HF (5 eq.)
Pr
(CH2Cl)2, 60 ºC, 9 h
O CF3
i
Y. 74%
Pr
Synthesis of Glycosyl Fluorides from (Phenylthio)glycosides4)
OAc
O
AcO
AcO
SPh
NPhth
P2140 (2 eq.)
CH2Cl2, rt, 2 h
OAc
O
AcO
AcO
F
NPhth
Y. 96% (β only)
Iodofluorination of Alkenes5)
R1
R2
I
P2140 (1.1 eq.)
KI or Sn
CH2Cl2, rt, 17 h
R2
R1
F
Y. 52-86 %
1) S. Hara, M. Monoi, R. Umemura, C. Fuse, Tetrahedron 2012, 68, 10145.
2) M. Kunigami, S. Hara, J. Fluorine Chem. 2014, 167, 101. 3) T. Inoue, C. Fuse, S. Hara, J. Fluorine Chem. 2015, 179, 48.
4) M. Kunigami, S. Hara, Carbohydr. Res. 2015, 417, 78.
5) S. Yano, S. Hara, Synthesis 2015, 2839.
P2140 IF5-Pyridine-HF (Fluorinating Reagent F-51)
1g / 5g / 25g
This reagent was merchandised under the tie-up with DAIKIN INDUSTRIES, LTD.
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