Perfluoroalkylation of unsaturated compounds in the presence of copper(II) salen complexes

Full text of DOI:10.1134/S1070428013030263

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 3, pp. 469–471. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.S. Kudyakova, D.N. Bazhin, Ya.V. Burgart, V.I. Saloutin, O.N. Chupakhin, 2013, published in Zhurnal Organicheskoi Khimii,
2013, Vol. 49, No. 3, pp. 481–482.
SHORT
COMMUNICATIONS
Dedicated to Full Member of the Russian Academy of Sciences
I.P. Beletskaya on her jubilee
Perfluoroalkylation of Unsaturated Compounds in the Presence
of Copper(II) Salen Complexes
Yu. S. Kudyakova, D. N. Bazhin, Ya. V. Burgart, V. I. Saloutin, and O. N. Chupakhin
Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. Akademicheskaya/S. Kovalevskoi 22/20, Yekaterinburg, 620990 Russia
e-mail: kud@ios.uran.ru
Received January 17, 2013
DOI: 10.1134/S1070428013030263
Introduction of perfluoroalkyl groups into mole-
cules of organic compounds essentially changes their
physicochemical properties and extends the scope of
their practical applications [1–3]. Organometallic ca-
talysis provides an important tool for performing per-
fluoroalkylation reactions, and variation of the reaction
conditions and ligand nature is a significant factor
affecting the yield and product structure [4–8]. For
example, catalysis of reactions of alkenes with per-
fluoroalkylating agents by copper(I) and copper(II)
salts in the presence of different ligands leads to the
formation of functionalized trifluoromethyl-substituted
compounds [4, 5].
fact, copper(II) complexes I and II efficiently cata-
lyzed reactions of perfluoroalkyl iodides IIIa and IIIb
with alkenes IV–VI and with propargyl alcohol VII,
and the corresponding addition products VIIIa, VIIIb,
IXb, Xb, XIa, and XIb were obtained in good yields
(70–91%) under mild conditions. No reaction occurred
in the absence of a catalyst and/or radical initiator.
Presumably, complexes I and II promote decom-
position of hydrogen peroxide to produce hydroxyl
radicals HO· which initiate radical addition of per-
fluoroalkyl iodides to unsaturated compounds. Com-
plex II ensured somewhat higher yields than did com-
plex I, i.e., the catalyst with a longer fluorinated
carbon chain is more efficient.
Perfluoroalkylation of unsaturated compounds
(genral procedure). Complex I, 5 mol %, was added to
a mixture of 0.10 mol of perfluoroalkyl iodide IIIa or
IIIb and 0.10 mol of unsaturated compound IV–VII in
30 ml of acetonitrile, 20 ml of 38% hydrogen peroxide
was then added dropwise, and the mixture was stirred
We previously synthesized transition metal salen
complexes, namely {ethyl 2-[2-(2-hydroxyphenyl-
methylideneamino)phenylaminatomethylidene]-3-oxo-
3-(polyfluoroalkyl)propionato}copper(II) I and II [9].
In the present communication we report on the use of
complexes I and II as catalysts in radical addition of
perfluoroalkyl iodides to unsaturated compounds. In
I
i
R
RF
R
RFI
+
H2C
70–91%
IIIa, IIIb
IV–VI
VIIIa, VIIIb, IXb, Xb
N
O
N
O
I
Cu
CO2Et
i
RF
OH
OH
RFI
+
HC
79–87%
R'
IIIa, IIIb
VII
XIa, XIb
I, II
RF = C4F9 (a), C3F7OCF(CF)3CF2OCF(CF3) (b); IV, VIII, R = OH; V, IX, R = OAc; VI, X, R = H(CH2)7; I, R′ = CF3;
II, R = H(CF2)2; i: MeCN, 38% H2O2, complex I or II (5 mol %), 25°C.
469

KUDYAKOVA et al.
470
for 2 h. The product was extracted into chloroform (3×
50 ml), the extract was washed with water and dried
over sodium sulfate, and the solvent was distilled off.
F 45.07. C18H20F17IO2. Calculated, %: C 30.10; H 2.81;
F 44.97.
4,4,5,5,6,6,7,7,7-Nonafluoro-2-iodohept-2-en-1-ol
(XIa). Yield 33.4 g (83%), reddish liquid, bp 105–
107°C (10 mm). H NMR spectrum (CDCl3), δ, ppm:
4,4,5,5,6,6,7,7,7-Nonafluoro-2-iodoheptan-1-ol
1
(VIIIa). Yield 28.3 g (70%), reddish oily substance,
1
2.28–2.54 br.s (1H, OH), 4.35–4.37 m (2H, CH2OH),
6.54 m, 6.77 m (1H, CH=). 19F NMR spectrum
(CDCl3), δF, ppm: 36.17 m (2F, γ-F, Z), 36.44 m (2F,
γ-F, E), 37.56 m (2F, β-F, Z), 37.95 m (2F, β-F, E),
50.25 m (2F, α-F, E), 54.11 m (2F, α-F, Z), 81.03 t.t
bp 97–98°C (10 mm). H NMR spectrum (CDCl3), δ,
ppm: 2.79 m and 3.08 m (1H each, CF2CH2), 3.76 m
19
(2H, CH2OH), 4.32 m (1H, CHI). F NMR spectrum
3
(CDCl3), δF, ppm: 35.95 q.t (2F, γ-F, JFF = 12.7,
3.8 Hz), 37.29 m (2F, β-F), 47.06 d.m and 49.86 d.m
4
3
2
(3F, CF3, E/Z, JFF = 9.7, JFF = 3.3 Hz). Found, %:
C 20.95; H 1.07; F 42.46. C7H4F9IO. Calculated, %:
C 20.91; H 1.00; F 42.53.
(1F each, CF2CH2, JFF = 270.9 Hz), 80.79 t.t (3F,
3
4
CF3, JFF = 9.7, JFF = 3.2 Hz). Found, %: C 20.55;
H 1.57; F 42.56. C7H6F9IO. Calculated, %: C 20.81;
H 1.50; F 42.32.
4,6,6,7,9,9,10,10,11,11,11-Undecafluoro-2-iodo-
4,7-bis(trifluoromethyl)-5,8-dioxaundec-2-en-1-ol
(XIb). Yield 50.1 g (79%), colorless liquid, bp 101–
4,6,6,7,9,9,10,10,11,11,11-Undecafluoro-2-iodo-
4,7-bis(trifluoromethyl)-5,8-dioxaundecan-1-ol
(VIIIb). Yield 45.8 g (72%), yellow liquid, bp 85–
1
103°C (10 mm). H NMR spectrum (CDCl3), δ, ppm:
1
2.28–2.54 br.s (1H, OH), 4.35–4.37 m (2H, CH2OH),
6.54 m and 6.77 m (1H, CH=). 19F NMR spectrum
(CDCl3), δF, ppm: 16.58 m (1F, CF), 32.09 s (2F,
CF3CF2), 32.62 m (1F, CFCH), 76.68 m (3F, CF3),
79.43 m (3F, CF2OCFCF2), 80.49 m (3F, CF3CF2),
81.78 m (3F, CF3CFCF2), 83.26 m (1F, OCFCF2).
Found, %: C 20.79; H 0.70; F 50.86. C11H4F17IO3. Cal-
culated, %: C 20.84; H 0.64; F 50.94.
87°C (10 mm). H NMR spectrum (CDCl3), δ, ppm:
2.79 m and 3.08 m (1H each, CF2CH2), 3.76 m (2H,
CH2OH), 4.32 m (1H, CHI). 19F NMR spectrum
(CDCl3), δF, ppm: 17.02 m (1F, CF), 30.61 m (1F,
CFCH2), 32.27 m (2F, CF3CF2), 78.71 d.m (3F, CF3,
3JFF = 42.3 Hz), 80.50 m (6F, CF3CF2CF2OCFCF2),
81.61 m (3F, CF3CFCF2), 82.02 m (1F, CFCF2).
Found, %: C 20.70; H 1.03; F 50.66. C11H6F17IO3. Cal-
culated, %: C 20.77; H 0.95; F 50.78.
The reactions of perfluoroalkyl iodides IIIa and
IIIb with alkenes IV–VI and propargyl alcohol (VII)
in the presence of complex II were carried out in
a similar way. Yield, %: 73 (VIIIa), 74 (VIIIb), 87
(IXb), 91 (Xb), 87 (XIa), 85 (XIb).
4,6,6,7,9,9,10,10,11,11,11-Undecafluoro-2-iodo-
4,7-bis(trifluoromethyl)-5,8-dioxaundecyl acetate
1
(IXb). Yield 54.2 g (80%), colorless liquid. H NMR
spectrum (CDCl3), δ, ppm: 2.10 s (3H, CH3), 2.83 m
and 2.99 m (1H each, CFCH2), 4.31 m (3H,
CHICH2O). 19F NMR spectrum (CDCl3), δF, ppm:
17.10 m (1F, CF), 30.59 m (1F, CFCH2), 32.33 m (2F,
CF3CF2), 78.75 d.m (3F, CF3, 3JFF = 42.3 Hz), 80.45 m
(6F, CF3CF2CF2OCFCF2), 80.57 m (3F, CF3CFCF2),
82.09 m (1F, CFCF2). Found, %: C 29.95; H 1.13;
F 47.77. C13H8F17IO4. Calculated, %: C 23.03; H 1.19;
F 47.63.
1
The H and 19F NMR spectra were recorded on
a Bruker DRX-400 spectrometer at 400 and 376 MHz,
respectively, using tetramethylsilane (1H) and hexa-
fluorobenzene (19F) as references. The elemental com-
positions were determined on a Perkin Elmer CHN PE
2400 analyzer. Initial perfluoroalkyl iodides IIIa and
IIIb were synthesized as described in [3, 10].
This study was performed under financial support
by the Ural Branch of the Russian Academy of
Sciences, program of the Presidium of the Russian
Academy of Sciences “Development of Methods for
the Synthesis of Chemical Compounds and Design of
New Materials” (project no. 12-P-1020).
1,1,1,2,2,3,3,5,6,6,8-Undecafluoro-10-iodo-5,8-
bis(trifluoromethyl)-4,7-dioxaoctadecane (Xb).
Yield 58.9 g (82%), colorless liquid, bp 115–119°C
1
(3 mm). H NMR spectrum (CDCl3), δ, ppm: 0.92 t
(3H, Me, = J 7.1 Hz), 1.28–1.62 m [14H, (CH2)7],
2.56–2.63 m (2H, CH2CI), 6.52 m, 6.72 m (1H,
CFCH). 19F NMR spectrum (CDCl3), δF, ppm: 17.10 m
(1F, CF), 30.59 m (1F, CFCH2), 32.33 m (2F, CF3CF2),
REFERENCES
1. Modern Fluoroorganic Chemistry, Kirsch, P., Ed.,
3
78.75 d.m (3F, CF3, JFF = 42.3 Hz), 80.45 m (6F,
Weinheim: Wiley–VCH, 2004, p. 308.
CF3CF2CF2OCFCF2), 80.57 m (3F, CF3CFCF2),
82.09 m (1F, CFCF2). Found, %: C 30.01; H 2.83;
2. Murphy, P.M., Baldwin, C.S., and Buck, R.C., J. Fluorine
Chem., 2012, vol. 138, p. 3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

PERFLUOROALKYLATION OF UNSATURATED COMPOUNDS
471
3. Bazhin, D.N., Gorbunova, T.I., Zapevalov, A.Ya.,
and Saloutin, V.I., J. Fluorine Chem., 2009, vol. 130,
p. 438.
7. Studer, A., Angew. Chem., Int. Ed., 2012, vol. 51,
p. 8950.
8. Macé, Y. and Magnier, E., Eur. J. Org. Chem., 2012,
4. Zhu, R. and Buchwald, S.L., J. Am. Chem. Soc., 2012,
vol. 13, p. 2479.
vol. 134, p. 12462.
9. Kudyakova, Yu.S., Goryaeva, M.V., Burgart, Ya.V., and
Saloutin, V.I., Izv. Akad. Nauk, Ser. Khim., 2010,
p. 1707.
10. Bazhin, D.N., Gorbunova, T.I., Zapevalov, A.Ya.,
Beketov, I.V., and Saloutin, V.I., Russ. J. Gen. Chem.,
2011, vol. 81, p. 1829.
5. Wang, X., Ye, Y., Zhang, S., Feng, J., Xu, Y., Zhang, Y.,
and Wang, J., J. Am. Chem. Soc., 2011, vol. 133,
p. 16410.
6. Besset, T., Schneider, C., and Cahard, D., Angew.
Chem., Int. Ed., 2012, vol. 51, p. 5048.
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