Nickel(0)-catalyzed fluoroalkylation of alkenes, alkynes, and aromatics with perfluoroalkyl chlorides

Article abstract of DOI:10.1021/jo010178j

Treatment of perfluoroalkyl chlorides (R_FCl) with alkenes, alkynes, or aromatics in the presence of 0.1 equiv of nickel dichloride, 1.5 equiv of zinc powder, and 0.4 equiv of triphenylphosphine in DMF at 95-100 °C for 6-8 h give the correspondi

Full text of DOI:10.1021/jo010178j

J . Org. Chem. 2001, 66, 4651-4656
4651
Nick el(0)-Ca ta lyzed F lu or oa lk yla tion of Alk en es, Alk yn es, a n d
Ar om a tics w ith P er flu or oa lk yl Ch lor id es
Xiao-Ting Huang and Qing-Yun Chen*
Laboratory of Fluorine Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, 200032, Shanghai, China
Chenqy@pub.sioc.ac.cn
Received February 15, 2001
Treatment of perfluoroalkyl chlorides (RFCl) with alkenes, alkynes, or aromatics in the presence of
0.1 equiv of nickel dichloride, 1.5 equiv of zinc powder, and 0.4 equiv of triphenylphosphine in
DMF at 95-100 °C for 6-8 h give the corresponding perfluoroalkylated products in good yields. A
single electron-transfer mechanism is suggested.
In tr od u ction
successfully applied to this reaction. Uniquely, it was
found that oxidant such as Pb(OAc)4, PbO2,28 Ce-
The addition reaction of perfluoroalkyl iodides (RFI)
and bromides (RFBr) to olefins, alkynes, or aromatics is
one of the most important methods for introducing
perfluoroalkyl group to organic compounds.1 Such a
process is traditionally accomplished with photo-
chemical,2-5 thermal,6 electrolytic,7 and free radical
initiations.8 Recently, however, some reductive systems
were found to be more effective. For example: metals,
transition metals,9,10 and inorganic reductants11 as well
as redox systems12 such as Cu,13,14 Zn,15 Mg,16 Ni,17 Fe,18
Pd,19,20 Pt,21 Fe(CO)4,22 Na2S2O4,23 thiourea dioxide,24
(NH4)2S2O8/HCO2Na,25 CrCl3/Fe,26 Co(II)/Zn,27 etc. were
(SO2)4•4H2O, (NH4)2Ce(NO3)6, Na2S2O8, (NH4)2S2O8, or
29
KMnO4 can also initiate the same addition reaction
even to fluorinated olefins.30 The results obtained by
using these initiators can be rationalized in terms of
single electron-transfer (SET) mechanism.9,10 Unfortu-
nately, all these initiation systems cannot be applied to
perfluoroalkyl chlorides (RFCl) because of their stronger
carbon-chlorine bonds. In fact, R-, ω-chloroperfluoroalkyl
iodides [Cl(CF2)nI, n g 2] have been used as substrates
in the reaction: the iodine being attacked, while the
chlorine inert.9-12 It was not until very recently that this
problem has been partially solved: using dimethyl sul-
foxide (DMSO) as a solvent instead of CH3CN/H2O in
Na2S2O4/NaHCO3 initiation system (so-called sulfinato-
dehalogenation reaction),11 perfluoroalkyl chlorides, ethyl
chlorofluoro-, chlorodifluoroacetates, even nonfluorinated
compounds, such as ethyl dichloro-, chloroacetates and
chloroform, can either be converted to the corresponding
sulfinate salts or alkylate alkenes, alkynes,31 and aro-
matics.32 The tremendous role of solvent encouraged us
to further reexamine the perfluoroalkylation of organic
compounds with perfluoroalkyl chlorides by means of
varous metals in different solvents. We, herein, present
the results of nickel(0)-catalyzed perfluoroalkylation of
alkenes, alkynes, and aromatics with perfluoroalkyl
chlorides.
(1) Chambers, R. D. Fluorine in Organic Chemistry; Wiley Inter-
science: New York, 1973. (b) Hudlicky, M. Chemistry of Organic
Fluorine Compounds, 2nd ed.; Ellis, Horwood: Chichester, England,
1976. (c) Hudlicky, M.; Pavlath, A. E. Chemistry of Organic Fluorine
Compounds II; ACS Monograph 187; American Chemical Society:
Washington, DC, 1995.
(2) Haszeldine, R. N. J . Chem. Soc. 1950, 3037.
(3) Haszeldine, R. N. J . Chem. Soc. 1951, 588.
(4) Haszeldine, R. N. J . Chem. Soc. 1953, 3761.
(5) Tiers, G. V. D. J . Org. Chem. 1962, 27, 2261.
(6) Chamber, R. D.; Hutschinson, J .; Mobbs, R. H.; Musgrave, W.
K. R. Tetrahedron 1964, 20497.
(7) Calas, P.; Moreau, P.; Commeyras, A. J . Chem. Soc., Chem.
Commun. 1982, 433.
(8) Baum, K.; Bedford, C. D.; Hunad, R. J . J . Org. Chem. 1982, 47,
2251 and references therein.
(9) For review, see: Chen, Q.-Y. Isr. J . Chem. 1999, 39, 179.
(10) For review, see: Chen, Q.-Y. Single electron-transfer reaction
of perfluoroalkyl iodides. In Organofluorine Chemistry in China;
Huang, W.-Y., Ed.; Shanghai Science and Technology Press: Shanghai,
1996; Chapter 5, p 112.
Resu lts a n d Discu ssion
(11) For review, see: Huang, W.-Y.; Lu, L. Sulfinatodehalogenation
reaction. In Organofluorine Chemistry in China; Huang, W.-Y., Ed.;
Shanghai Science and Technology Press: Shanghai, 1996; Chapter 8,
p 203.
(12) For review, see: Hu, C.-M.; Qing, F.-L.; Qiu, Y.-L. The applica-
tion of oxidation-reduction system in organofluorine chemistry. In
Organofluorine Chemistry in China; Huang, W.-Y., Ed.; Shanghai
Science and Technology Press: Shanghai, 1996; Chapter 7, p 175.
(13) Chen, Q.-Y.; Yang, Z.-Y. J . Fluorine Chem. 1985, 28, 399.
(14) Chen, Q.-Y.; Yang, Z.-Y.; He, Y.-B. J . Fluorine Chem. 1987, 37,
171.
In 1986 we carried out the addition reaction of R-,
ω-chloroperfluoroalkyl iodides [Cl(CF2)nI, n ) 4, 6] to
(20) Chen, Q.-Y.; Yang, Z.-Y.; Zhao, C.-X. J . Chem. Soc., Perkin
Trans. 1 1988, 563.
(21) Chen, Q.-Y.; Yang, Z.-Y. Youji Huaxue 1986, 41.
(22) Fuchikami, T.; Ojima, I. Tetrahedron Lett. 1984, 25, 303.
(23) Huang, W.-Y.; Huang, B.-N.; Wang, W. Acta Chim. Sinica 1983,
41, 1193.
(24) Huang, W.-Y.; Zhang, J .-L. Chin. Chem. Lett. 1990, 191.
(25) Hu, C.-M.; Qiu, Y.-L.; Qing, F.-L. J . Fluorine Chem. 1991, 51,
295.
(15) Chen, Q.-Y.; Yang, Z.-Y.; Qiu, Z.-M. Kexue Tongbao 1988, 33,
1453 (Eng. ed. 1988, 22, 1866).
(16) Chen, Q.-Y.; Qiu, Z.-M.; Yang, Z.-Y. J . Fluorine Chem. 1988,
36, 149.
(17) Chen, Q.-Y.; Yang, Z.-Y. J . Chem. Soc., Chem. Commun. 1986,
498.
(18) Chen, Q.-Y.; He, Y.-B.; Yang, Z.-Y. J . Fluorine Chem. 1986, 34,
255.
(19) Chen, Q.-Y.; Yang, Z.-Y. Acta Chim. Sinica 1986,44, 1025.
(26) Hu, C.-M.; Qiu, Y.-L. Tetrahedron Lett. 1991, 32, 4001.
(27) Hu, C.-M.; Qiu, Y.-L. J . Org. Chem. 1992, 57, 2339.
(28) Chen, Q.-Y.; Chen, J .-G. Acta Chim. Sinica 1988, 40, 307.
(29) Guo, X.-C.; Chen, Q.-Y. J . Fluorine Chem. 1998, 88, 63.
(30) Li, A.-R.; Chen, Q.-Y. Synthesis 1997, 1481.
(31) Long, Z.-Y.; Chen, Q.-Y. J . Org. Chem. 1999, 64, 4775.
(32) Long, Z.-Y.; Chen, Q.-Y. Acta Chim. Sinica 2000, 6, 713.
10.1021/jo010178j CCC: $20.00 © 2001 American Chemical Society
Published on Web 05/24/2001

4652 J . Org. Chem., Vol. 66, No. 13, 2001
Huang and Chen
Ta ble 1. Rea ction of RF Cl w ith Electr on -Rich Alk en es
(2) In d u ced by Ni(0) in th e P r esen ce or Absen ce of P h 3P
in DMF a
Sch em e 1
entry RFClb alkenes T °C time (h)
3 yield % (no PPh3)c
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1a
2a
2b
2c
2f
2a
2b
2c
2d
2f
2a
2b
2c
2e
2f
95
100
100
95
95
100
95
100
95
95
100
95
100
95
8
7
6
7
8
7
6
6
7
7
7
6
6
8
72 (29)
75 (31)
70 (cis/trans ) 70:30) (25)d
63 (15)
70 (31)
73 (27)
Sch em e 2
Sch em e 3
Sch em e 4
1b
70 (cis/trans ) 70:30) (25)d
71 (30)
62 (15)
74 (30)
75 (28)
1c
70 (cis/trans ) 70:30) (24)d
78 (27)
62 (14)
a
b
1/2/Zn/NiCl2/PPh3 ) 1:1.5:1.5:0.1:0.4. The conversion of RFCl
was 100% (determined by 19F NMR). c The isolated yields were
based on RFCl and a trace of RFH was also obtained; the yields in
the bracket were obtained in HMPA in the absence of PPh3, RFH
d
(g40%) being the major products. The ratio of cis/trans based
on 1H NMR.
Ta ble 2. Rea ction of RF Cl w ith Electr on -P oor Alk en es
(4) In d u ced by Ni(0) in th e P r esen ce or Absen ce of P h 3P
in DMF a
entry RFClb alkenes T °C time (h) 5 yields % (no PPh3)c
1
2
3
4
5
6
1a
1b
1c
4a
4b
4a
4b
4a
4b
95
100
95
100
95
8
8
7
8
8
7
67 (30)
71 (27)
64 (25)
70 (30)
65 (28)
68 (28)
1:1.5:1.5:0.1:0.4) at 95-100 °C for 6-8 h to give the
corresponding chlorine-free adducts (3) in good yields (see
Scheme 1).
The addition products 3a c, 3bc, and 3cc, from the
perfluoroalkyl chlorides and 2c, are the tetrahydrofuran
derivatives, indicative of a free radical intermediate.10,13
The cis- and trans-configuration of 3a c, 3bc, and 3cc can
be assigned by comparing 1H NMR chemical shift of
-CH3 (cis < trans) (see Scheme 2). All the results are
listed in Table 1.
2. P er flu or oa lk yla tion of Electr on -P oor Alk en es
w ith P er flu or oa lk yl Ch lor id es. Different from the
previous DMSO-induced sulfinatodehalogenation method,31
we found that perfluoroalkyl chlorides can react not only
with electron-rich alkenes but also with electron-poor
ones under the similar conditions. Thus, when perfluo-
roalkyl chlorides (1) were treated with electron-deficient
alkenes (4) in DMF in the presence of zinc powder,
catalytic amounts of nickel dichloride and triphenylphos-
phine under nitrogen, hydrofluoroalkylated adducts (5)
were obtained in good yields (see Scheme 3). The results
are listed in Table 2.
3. P er flu or oa lk yla tion of Alk yn es w ith P er flu or o-
a lk yl Ch lor id es. Similarly, treatment of alkynes with
perfluoroalkyl chlorides in the presence of Zn/NiCl2/PPh3
(1.5:0.1:0.4) in DMF at 95-100 °C under nitrogen for 7-8
h gave the corresponding of E/Z mixture of alkenes in
50-75% yields (see Scheme 4). The E- and Z-isomers
were determined by comparing the chemical shifts of the
RF′CF 2CHdCHR in their respective 19F NMR spectra, the
downfield signal being assigned to the Z-isomer and the
upfield signal being assigned to the E-isomer.31,37 The
results are listed in Table 3.
100
a
b
1/2/Zn/NiCl2/PPh3 ) 1:1.5:1.5:0.1:0.4. The conversion of RFCl
was 100% (determined by 19F NMR). c The isolated yields were
based on RFCl and a trace of RFH was also obtained; the yields in
the bracket were obtained in HMPA in the absence of PPh3, RFH
(g40%) being the major products.
olefins in the presence of Raney nickel in EtOH at 80 °C
to give the iodine adducts in high yields.17 Later, Zhou
and Huang showed that the ω-chloro perfluoroalkylation
of amines,33 anilines,34 furan, thiophene and pyrrole35
with the same iodides can occur in the presence of
tetrakis(triphenylphosphine) nickel. Besides the easy
hydrogenation with Zn/NiCl2 in DMF at 80-120 °C,
perfluoroalkyl chloride is hardly functionalized by other
groups.31,36 Surprisingly, in HMPA, the addition reaction
of RFCl to alkenes did take place in the presence of Zn/
NiCl2 at 100 °C for 8 h despite of the low yields of the
adducts (15-30%), RFH being the major products (g
40%). The results are listed in Table 1 and Table 2. After
many attempts, it was found that the undesired RFH
could be suppressed significantly, subsequently raising
the yields of the adducts if 0.4 equiv of PPh3 was added
to the reaction mixture. Additionally, DMF can be used
instead of carcinogenic HMPA in the reaction.
1. P er flu or oa lk yla tion of Electr on -Rich Alk en es
w ith P er flu or oa lk yl Ch lor id es. It was found that
perfluoroalkyl chlorides (1) can smoothly react with
electron-rich alkenes (2) in DMF in the presence of zinc
powder and catalytic amount of nickel dichloride and
triphenylphosphine under nitrogen (1:2:Zn:NiCl2:PPh3 )
4. P er flu or oa lk yla tion of Ar om a tics w ith P er -
flu or oa lk yl Ch lor id es. Perfluoroalkylation of electron-
rich aromatic compounds (8) could be accomplished with
(33) Huang, Y. Z.; Zhou, Q. L. J . Org. Chem. 1987, 52, 3552.
(34) Zhou, Q.-L.; Huang, Y.-Z. J . Fluorine Chem. 1988, 39, 87.
(35) Zhou, Q.-L.; Huang, Y.-Z. J . Fluorine Chem. 1989, 43, 385.
(36) Chen, Q.-Y.; Wu, J .-P. Chin. J . Chem. 1991, 9, 181.
(37) Chen, J .; Hu, C.-M. Chin. J . Chem. 1994, 12, 468.

Nickel(0)-Catalyzed Fluoroalkylation
J . Org. Chem., Vol. 66, No. 13, 2001 4653
Ta ble 3. Rea ction of RF Cl w ith Alk yn es (6) In d u ced by
Ni(0) in DMF a
Sch em e 6
entry RFClb alkynes T °C time (h) 7 Z/Ec 7 yield %d
1
2
3
4
5
6
7
8
9
1a
6a
6c
6d
6e
6a
6b
6d
6a
6e
100
100
95
95
95
100
95
100
95
7
7
8
7
8
7
7
8
7
34/66
33/67
40/60
0/100
34/66
34/66
50/50
33/67
0/100
73
72
65
56
72
74
63
75
51
1b
1d
a
b
1/2/Zn/NiCl2/PPh3 ) 1:1.5:1.5:0.1:0.4. The conversion of RFCl
was 100% (determined by 19F NMR). c The ratio of Z/E was
determined by 19F NMR. The isolated yields were based on RFCl
d
Both the inhibition experiments and the formation of
tetrahydrofuran derivatives from the reaction with diallyl
ether indicated that the perfluoroalkyl radical might be
involved in the reaction mechanism. The most likely
explanation of generation of RF• is that RFCl, quite
similar to RFI,9-12 accepts one electron from Ni(0) com-
plex, produced by reaction of nickel dichloride with zinc
and triphenylphosphine, then dissociated to give RF• and
Cl-. The RF• adds to alkene to form intermediate A. The
intermediate, A, does not abstract chlorine from RFCl due
to the strong carbon-chlorine bond but easily picks a
hydrogen from the solvents to afford the adduct. Along
with the H-abstraction from the solvent to give RFH,38
RF• can be reduced by SET to form RF-, which is then
protonated to yield the same hydride. The one-electron
reduction of intermediate A to produce carbanion A-,
then the adduct, after protonation, seemingly, is less
important because the electron-accepting ability of A
should be much weaker than that of RF•. Similarly, the
RF• undergoes the addition reactions to alkynes and
aromatic compounds to afford perfluoroalkylated alkenes
and substituted aromatic compounds, respectively (see
Scheme 6).
The reason the formation of RFH can be suppressed
by adding Ph3P is not very clear yet. Some interaction
among protons Ph3P and RF• is expected to evaluate in
this system. However, it is known that the big ligand
(Ph3P) role is played in the formation of highly active
teriary phosphine complexes of Ni(0) and the proper
environment for both C-Cl bond activation and further
functionalization.39
In conclusion, we have developed a new practical
perfluoroalkylation method of alkenes, alkynes, and
aromatics with available perfluooroalkyl chlorides in the
presence of Ni(0).
and a trace of RFH was also obtained.
Sch em e 5
Ta ble 4. Rea ction of RF Cl w ith Ar om a tics (8) In d u ced
by Ni(0) in DMF a
entry RFClb ArH (8) T °C time (h)
products (9)c
yield %d
1
1a
8a
100
8
9a a
62
(o/p/m ) 44:38:18)
9a b
9a c
9a d
9a e
9bd
9be
9d a
2
3
4
5
6
7
8
8b
8c
8d
8e
8d
8e
8a
100
95
95
95
95
7
8
6
7
6
8
8
65
56
78
70
75
68
71
1b
1d
95
100
(o/p/m ) 48:32:20)
9
10
11
12
8b
8c
8d
8e
100
95
95
8
7
6
7
9d b
9d c
9d d
9d e
60
58
76
70
95
a
b
1/2/Zn/NiCl2/PPh3 ) 1:1.5:1.5:0.1:0.4. The conversion of RFCl
was 100% (determined by 19F NMR). c The position of perfluoro-
alkyl group located was determined by 19F NMR. The isolated
d
yields were based on RFCl and a trace of RFH was also obtained.
moderate to good yields in similar fashion with per-
fluoroalkyl chlorides in DMF in the presence of Zn/NiCl2/
PPh3 (1.5:0.1:0.4) under nitrogen at 95-100 °C (see
Scheme 5). The results are listed in Table 4.
The results in Table 4 are consistent with the electro-
philic property of perfluoroalkyl radical. The yields and
regioselectivity of the products were depended on the
structures of the starting aromatics. For example, with
anisole (8a ), a mixture of o-, p-, and m- was obtained,
while with N,N-dimethyl aniline (8b) only p-perfluoro-
alkylated products were isolated. The perfluoroalkyl
group was located on the o-position relative to -NH2 in
the reaction with p-aminoanisole (8c). When pyrrole (8d )
was used as substrate, only 2-perfluoroalkylated products
were obtained in good yields.
Exp er im en ta l Section
1H NMR spectra were recorded at 300 or 400 MHz on a
machine using TMS as an internal standard (positive for
upfield). 19F NMR spectra were recorded at 282 or 376 MHz
using CF3COOH as an external standard (positive for upfield).
The solvent for NMR measurement was CDCl3 or CD3COCD3.
1. Typ ica l P r oced u r e for th e Rea ction of 1 w ith 2. A
25 mL three-necked flask, equipped with a water condenser
5. In h ibitor a n d Mech a n ism Con sid er a tion . Before
the mechanism consideration, some inhibition experi-
ments were carried out. Addition of ET scavenger, i.e.,
p-dinitrobenzene (DBN) (20mol %), or free radical inhibi-
tor, i.e., hydroquinone (HQ) (20mol %), to the reaction
mixture of 1a and 2b decreased the conversion of 1a
significantly (from 90% without DNB to 0% and from 61%
without HQ to 35%) at the same reaction temperature
and time.
(38) We thank the Referee for reminding us of the possibility of the
formation of RFH from the reduction of RF• to RF followed by the
protonation along with the H-abstraction from the solvent. Indeed, a
previous report showed that both processes are of comparable impor-
tance for the CF3• radicals produced upon electrochemical reduction
of CF3Br in DMSO: Andreux, C. P.; Gelis, L.; Medebielle, M.; Pinson,
J .; Saveant, J . M. J . Am. Chem. Soc. 1990, 112, 3509.
(39) Grushin V. V.; Alper, H. Activation of otherwise unreactive
C-Cl bonds. In Activation of Unreactive Bonds and Organic Synthesis;
Murai, S., Ed.; Springer: Berlin, 1999; p 195, p 203.
-

4654 J . Org. Chem., Vol. 66, No. 13, 2001
Huang and Chen
and a magnetic stirring bar, was charged with zinc powder
(488 mg, 7.5 mmol), nickel dichloride (65 mg, 0.5 mmol), and
triphenylphosphine (530 mg, 2.0 mmol). The flask was filled
with nitrogen and the nitrogen purged solvent DMF (10 mL)
was then added. The mixture was heated to about 95 °C to
form a brown catalyst. A mixture of 1a (1.77 g, 5 mmol) and
2a (630 mg, 7.5 mmol) was added and stirred at this temper-
ature for 8 h. The conversion of 1a was 100%, determined by
19F NMR. After cooled, the precipitate was filtered off and the
product was extracted with ether. The combined extracts were
washed with water and dried over Na2SO4. After removing
ether, the residue was subjected to flash chromatography on
silica gel to give 3a a as a colorless oil (1.45 g, yield 72%).
3a a : colorless oil; 1H NMR δ 0.90 (t, J ) 6.6 Hz, 3H), 1.28-
1.42 (m, 6H), 1.54-1.64 (m, 2H), 1.96-2.14 (m, 2H); 19F NMR
δ 4.0 (t, J ) 10 Hz, 3F), 37.6 (m, J ) 15 Hz, 2F), 45.1 (s, 2F),
46.1 (s, 2F), 46.8 (s, 2F), 49.4 (s, 2F); MS m/z (relative intensity)
403 (M+ - 1, 0.89), 389 (1.68), 85 (47.10), 71 (26.52), 69 (16.63),
57 (70.46), 43 (100.00); HRMS calcd for C12H13F13: 404.0809,
Found: 404.0768.
3ca :31 colorless oil; 1H NMR δ 0.88 (t, J ) 6.5 Hz, 3H), 1.29-
1.65 (m, 8H), 1.96-2.13 (m, 2H), 6.02 (tt, J ) 52, 5.2 Hz, 1H);
19F NMR δ 37.8 (t, J ) 15 Hz, 2F), 45.2 (s, 2F), 46.9 (s, 4F),
53.1 (s, 2F), 60.5 (d, J ) 52 Hz, 2F); MS m/z (relative intensity)
386 (M+, 0.24), 385 (M+ - 1, 1.63), 371 (3.95), 85 (30.98), 71
(20.60), 57 (68.75), 43 (100.00).
3cb:31 colorless oil; 1H NMR δ 0.89 (t, J ) 6 Hz, 3H), 1.29-
1.65 (m, 12H), 1.95-2.13 (m, 2H), 6.03 (tt, J ) 52, 5.2 Hz,
1H);19F NMR δ 38.3 (t, 2F), 45.5 (s, 2F), 47.5 (s, 4F), 53.8 (s,
2F), 61.3 (d, 2F); MS m/z (relative intensity) 413 (M+ - 1),
385 (3.42), 371 (2.52), 101 (2.46), 85 (7.19), 71 (31.45), 57
(59.11), 43 (100.00).
3cc:31 colorless oil; 1H NMR δ 0.97 (d, J ) 7.0 Hz, 0.7 × 3H,
cis-CH3), 1.07 (d, J ) 6.5 Hz, 0.3 × 3H, trans-CH3), 1.93-2.63
(m, 4H), 3.34-3.54 (m, 2H), 3.92-4.12 (m, 2H) 6.05 (tt, J )
52, 5.2 Hz, 1H); 19F NMR δ 35.1-38.3 (m, 2F), 45.0 (s, 2F),
46.7 (s, 4F), 52.7 (s, 2F), 60.2 (d, J ) 52 Hz, 2F); MS m/z
(relative intensity) 401 (M+ + 1, 18.31), 400 (M+, 2.38), 399
(M+ - 1, 11.22), 383 (18.03), 370 (13.70), 69 (100.00), 55 (74.65),
41 (47.32).
3ce: colorless oil; 1H NMR δ 1.72-2.10 (m, 5H), 2,24-2.44
(m, 2H), 4.17 (t, J ) 6.3 Hz, 2H), 6.84 (tt, J ) 51, 5.3 Hz,
1H);19F NMR δ 38.2 (s, 2F), 45.5 (s, 2F), 47.4 (s, 4F), 53.6 (s,
2F), 61.4 (d, 2F); MS m/z (relative intensity) 403 (M+ + 1,
29.50), 91 (7.34), 73 (4.29), 61 (23.67), 51 (10.91), 43 (100.00).
Anal. Calcd for C11H10F12O2: C, 32.84; H, 2.49. Found: C,
32.76; H: 2.29.
3a b: colorless oil; 1H NMR δ 0.89 (t, J ) 5.8 Hz, 3H), 1.28-
1.64 (m, 12H), 2.02-2.13 (m, 2H); 19F NMR δ 3.98 (t, J ) 10
Hz, 3F), 37.6 (m, J ) 15 Hz, 2F), 45.1 (s, 2F), 46.1 (s, 2F), 46.8
(s, 2F), 49.4 (s, 2F); MS m/z (relative intensity) 431 (M+ - 1,
0.91), 389 (14.48), 85 (12.80), 71 (44.32), 69 (18.03), 57 (95.06),
43 (100.00); HRMS calcd for C14H17F13
432.1104.
: 432.1122, Found:
3a c: colorless oil; 1H NMR δ 1.01 (d, J ) 6.6 Hz, 0.7 × 3H,
cis-CH3), 1.09 (d, J ) 6.6 Hz, 0.3 × 3H, trans-CH3), 1.95-2.46
(m, 4H), 3.35-3.56 (m, 2H), 3.94-4.13 (m, 2H); 19F NMR δ
3.90 (t, J ) 10 Hz, 3F), 36.7 (m, 2F), 45.0 (s, 2F), 46.1 (s, 2F),
46.7 (d, J ) 9 Hz, 2F), 49.4 (d, J ) 9 Hz, 2F); MS m/z (relative
intensity) 418 (M+, 0.85), 388 (52.77), 69 (100.00), 55 (74.16),
41 (34.19); Anal. Calcd for C12H11F13O: C, 34.45; H, 2.63.
Found: C, 34.59; H, 2.66.
3a f: colorless oil; 1H NMR δ 1.15-2.16 (m, 11H); 19F NMR
δ 4.0 (t, J ) 9.4 Hz, 3F), 41.3 (d, J ) 10.2 Hz, 2F), 43.8 (s, 2F),
45.3 (s, 2F), 46.0 (d, 2F), 49.4 (d, J ) 12.7 Hz, 2F); MS m/z
(relative intensity) 402 (M+, 10.77), 401 (75.42), 381 (48.91),
3cf:31 colorless oil; 1H NMR δ 1.18-2.14 (m, 11H), 6.04 (tt,
J ) 52, 5.2 Hz, 1H);19F NMR δ 41.3 (dd, J ) 7.2, 3.6 Hz, 2F),
43.8 (s, 2F), 45.3 (s, 2F), 46.7 (s, 2F), 52.9 (s, 2F), 60.3 (d, J )
52 Hz, 2F); MS m/z (relative intensity) 383 (M+ - 1, 1.62),
382 (3.68), 363 (3.67), 345 (10.83), 83 (100.00), 55 (48.80), 51
(35.77), 41 (29.89).
2. Gen er a l P r oced u r e for th e Rea ction of 1 w ith 4. A
25 mL three-necked flask, equipped with a water condenser
and a magnetic stirring bar, was charged with zinc powder
(488 mg, 7.5 mmol), nickel dichloride (65 mg, 0.5 mmol), and
triphenylphosphine (530 mg, 2.0 mmol). The flask was filled
with nitrogen and the nitrogen purged solvent DMF (10 mL)
was then added. The mixture was heated to about 95 °C to
form a brown catalyst. A mixture of 1a (1.77 g, 5 mmol) and
4a (398 mg, 7.5 mmol) was added and stirred at this temper-
ature for 8 h. The conversion of 1a was 100%, determined by
19F NMR. After it was cooled, the precipitate was filtered off
and the product was extracted with ether. The combined
extracts were washed with water and dried over Na2SO4. After
removal of ether, the residue was subjected to flash chroma-
tography on silica gel to give 5a a as a colorless oil (1.25 g,
yield 67%).
81 (100.00), 69 (25.01), 41 (53.26). Anal. Calcd for C12H11F13
:
C, 35.82; H, 2.74; F, 61.44. Found: C, 35.87; H, 2.93; F, 61.30.
3ba :31 colorless oil; 1H NMR δ 0.91 (t, J ) 6.7 Hz, 3H), 1.31-
1.66 (m, 8H), 1.98-2.16 (m, 2H), 6.06 (tt, J ) 52, 5.6 Hz, 1H);
19F NMR δ 37.4 (t, J ) 12 Hz, 2F), 48.7 (s, 2F), 53.3 (m, J )
5 Hz, 2F), 60.4 (d, J ) 45 Hz, 2F); MS m/z (relative intensity)
286 (M+, 1.25), 285 (M+ - 1, 10.70), 284 (12.83), 271 (20.41),
85 (100.00), 71 (36.63), 57 (60.83), 43 (24.73).
3bb:31 colorless oil; 1H NMR δ 0.9 (t, J ) 6.6 Hz, 3H), 1.55-
1.65 (m, 2H),1.29-1.44 (m, 10H), 1.97-2.15 (m, 2H), 6.04 (tt,
J ) 52, 5.6 Hz, 1H); 19F NMR δ 36.7 (s, 2F), 48.3 (s, 2F), 52.8
(s, 2F), 59.9 (d, 2F); MS m/z (relative intensity) 314 (M+, 0.82),
313 (M+ - 1, 5.28), 271 (34.97), 85 (6.46), 71 (19.86), 57
(100.00), 43 (59.78).
1
5a a : colorless oil; H NMR δ 2.43-2.73 (m, 4H); 19F NMR
δ 4.1 (t, J ) 10 Hz, 3F), 38.6 (m, 2F), 45.1 (s, 2F), 46.1 (s, 2F),
46.7 (s, 2F), 49.5 (s, 2F); MS m/z (relative intensity) 373 (M+,
0.76), 343 (10.54), 149 (15.42), 104 (47.63), 69 (37.31), 54
(100.00); Anal. Calcd for C9H4F13N: C, 28.95; H, 1.07; N, 3.75;
F, 66.22. Found: C, 28.94; H, 0.97; N, 3.77; F, 66.13.
5a b: colorless oil; 1H NMR δ 1.35 (t, J ) 7.0 Hz, 6H), 1.93-
2.49 (m, 4H), 4.15 (m, 4H); 19F NMR δ 4.0 (t, J ) 9.5 Hz, 3F),
38.6 (t, J ) 5 Hz, 2F), 45.1 (s, 2F), 46.1 (s, 2F), 46.6 (s, 2F),
49.4 (s, 2F); MS m/z (relative intensity) 484 (M+, 1.34), 429
(38.17), 169 (45.04), 97 (31.02), 70 (100.00), 69 (73.81); Anal.
Calcd for C12H14F13O3P: C, 29.75; H, 2.89. Found: C, 29.77;
H, 3.00.
3bc:31 colorless oil; 1H NMR δ 0.98 (d, J ) 7.0 Hz, 0.7 ×
3H, cis-CH3), 1.09 (d, J ) 6.6 Hz, 0.3 × 3H, trans-CH3), 1.95-
2.64 (m, 4H), 3.35-3.55 (m, 2H), 3.94-4.13 (m, 2H), 6.05 (tt,
J ) 52, 5.5 Hz, 1H); 19F NMR δ 34.9-38.2 (m, 2F), 48.6 (s,
2F), 52.9 (s, 2F), 60.3 (d, J ) 51.5 Hz, 2F); MS m/z (relative
intensity) 301 (M+ + 1, 62.44), 299 (31.75), 283 (38.97), 270
(46.68), 69 (100.00), 55 (82.65), 51 (20.49), 41 (52.19).
1
3bd : colorless oil; H NMR δ 1.81-2.30 (m, 5H), 3.73 (t, J
) 6.2 Hz, 2H), 6.05 (tt, J ) 52, 5.5 Hz, 1H);19F NMR δ 32.7
(m, 2F), 44.1 (d, J ) 6.8 Hz, 2F), 48.7 (t, J ) 5 Hz, 2F), 57.0
(d, J ) 50 Hz, 2F); MS m/z (relative intensity) 260 (M+, 1.89),
259 (M+ - 1, 13.07), 243 (9.77), 223 (100.00), 177 (59.78), 151
(39.61), 109 (83.25), 101 (35.85), 91 (73.07), 77 (52.57), 59
(65.46), 51 (96.57), 47 (57.14). Anal. Calcd for C7H8F8O: C,
32.31; H, 3.08; F, 58.46. Found: C, 32.00; H, 3.28; F, 58.48.
3bf:31 colorless oil; 1H NMR δ 1.17-2.17 (m, 11H), 6.02 (tt,
J ) 52, 5.6 Hz, 1H); 19F NMR δ 41.1 (t, J ) 4.2 Hz, 2F), 46.0
(d, J ) 6.6 Hz, 2F), 50.7 (m, J ) 6 Hz), 60.6 (d, J ) 52 Hz,
2F); MS m/z (relative intensity) 284 (M+, 0.63), 283 (M+ - 1,
5.65), 263 (4.05), 245 (7.90), 113 (9.53), 83 (100.00), 56 (12.02),
55 (59.71), 51 (22.12), 41 (36.18).
5ba : colorless oil; 1H NMR δ 2.62-2.99 (m, 4H), 6.73 (tt, J
) 51, 5.6 Hz, 1H);19F NMR δ 33.7 (m, 2F), 44.0 (s, 2F), 48.4
(d, J ) 4 Hz, 2F), 57.0 (d, J ) 49.5 Hz, 2F); MS m/z (relative
intensity) 256(M+ + 1, 1.68), 166 (15.28), 104 (100.00), 69
(26.62), 55 (22.38), 54 (93.74), 51 (71.48), 41 (37.17). Anal.
Calcd for C7H5F8N: C, 32.94; H, 1.96. Found: C, 33.01; H,
2.02.
1
5bb: colorless oil; H NMR δ 1.32 (m, 6H), 1.98-2.50 (m,
4H), 4.14 (m, 4H), 6.77 (tt, J ) 51, 5.5 Hz, 1H);19F NMR δ
33.6 (m, 2F), 43.8 (s, 2F), 48.5 (d, J ) 4 Hz, 2F), 57.0 (d, J )
52 Hz, 2F); MS m/z (relative intensity) 367 (M+ + 1, 13.57),
339 (7.08), 311 (8.75), 293 (2.18), 165 (6.15), 109 (2.81), 51

Nickel(0)-Catalyzed Fluoroalkylation
J . Org. Chem., Vol. 66, No. 13, 2001 4655
(4.51); Anal. Calcd for C10H15F8O3P: C, 32.79; H, 4.10.
Found: C, 32.76; H, 4.40.
MS m/z (relative intensity) 326 (M+, 4.27), 297 (25.65), 70
(50.12), 69 (48.68), 56 (77.91), 55 (52.22), 43 (100.00), 41
(45.91); HRMS calcd for C13H18F8: 326.1280, Found: 326.1287.
7bd :31 colorless oil; 1H NMR δ 5.72-6.23 (m, 3H), 7.09-
7.48 (m, 5H); 19F NMR δ 28.35 (d, J ) 8.4 Hz, 0.5 × 2F, Z),
34.2 (d, J ) 10.3 Hz, 0.5 × 2F, E), 48.2 (s, 2F), 58.9 (s, 2F),
60.4 (d, J ) 52 Hz, 2F); MS m/z (relative intensity) 304 (M+,
15.74), 153 (100.00), 133 (76.81), 51 (15.14).
7d a : colorless oil; 1H NMR δ 0.91 (t, J ) 6.7 Hz, 3H), 1.29-
2.31 (m, 8H), 5.52-6.48 (m, 2H); 19F NMR δ 3.92 (t, J ) 9.8
Hz, 3F), 29.8 (d, J ) 13 Hz, 0.33 × 2F, Z), 34.4 (d, J ) 11.2
Hz, 0.67 × 2F, E), 44.6 (s, 2F), 45.1 (s, 4F), 45.9 (s, 2F), 46.7
(s, 2F), 49.3 (s, 2F); MS m/z (relative intensity) 516 (M+, 8.39),
440 (49.66), 169 (7.81), 121 (98.86), 82 (71.90), 70 (79.83), 69
(70.86), 56 (100.00), 55 (89.21), 41 (89.21); HRMS calcd for
5ca : colorless oil; 1H NMR δ 2.43-2.72 (m, 4H), 6.06 (tt, J
) 51.8, 5.1 Hz, 1H); 19F NMR δ 38.7 (q, J ) 15 Hz, 2F), 45.2
(d, J ) 10.7 Hz, 2F), 46.8 (s, 4F), 52.8 (s, 2F), 60.5 (d, J ) 52
Hz, 2F); MS m/z (relative intensity) 356 (M+ + 1, 2.86), 286
(10.85), 104 (96.11), 69 (18.33), 54 (100.00), 51 (44.40); Anal.
Calcd for C9H5F12N: C, 30.42; H, 1.41; N, 3.94; F, 64.22.
Found: C, 30.43; H, 1.49; N, 3.96; F, 64.80.
1
5cb: colorless oil; H NMR δ 1.32 (m, 6H), 1.97-2.47 (m,
4H), 4.15 (m, 4H), 6.88 (tt, J ) 50.8, 5.3 Hz, 1H); 19F NMR δ
37.6 (s, 2F), 44.6 (s, 2F), 46.1 (s, 4F), 52.2 (s, 2F), 61.1 (d, 2F);
MS m/z (relative intensity) 467 (M+ + 1, 83.46), 439 (33.33),
411 (100.00), 393 (25.34), 353 (15.08), 165 (41.80), 138 (23.35),
109 (43.74), 81 (26.98), 65 (28.31), 51 (34.83); Anal. Calcd for
C
12H15F12O3P: C, 30.90; H, 3.22. Found: C, 30.89; H, 3.33.
C
15H13F17: 516.0745, Found: 516.0752.
3. Gen er a l P r oced u r e for th e Rea ction of 1 w ith 6. A
7d e: colorless oil; 1H NMR δ 3.42 (s, 3H), 4.09 (m, 2H), 5.93
25 mL three-necked flask, equipped with a water condenser
and a magnetic stirring bar, was charged with zinc powder
(488 mg, 7.5 mmol), nickel dichloride (65 mg, 0.5 mmol), and
triphenylphosphine (530 mg, 2.0 mmol). The flask was filled
with nitrogen and the nitrogen purged solvent DMF (10 mL)
was then added. The mixture was heated to about 100 °C to
form a brown catalyst. A mixture of 1a (1.77 g, 5 mmol) and
6a (720 mg, 7.5 mmol) was added and stirred at this temper-
ature for 7 h. The conversion of 1a was 100%, determined by
19F NMR. After cooled, the precipitate was filtered off and the
product was extracted with ether. The combined extracts were
washed with water and dried over Na2SO4. After removing
ether, the residue was subjected to flash chromatography on
silica gel to give 7a a as a colorless oil (1.52 g, yield 73%).
7a a : colorless oil; 1H NMR δ 0.85 (t, J ) 6.5 Hz, 3H), 1.23-
1.57 (m, 6H), 2.10-2.28 (m, 2H), 5.40-6.41 (m, 2H); 19F NMR
δ 4.24 (t, J ) 9.6 Hz, 3F), 30.0 (d, J ) 12.7 Hz, 0.34 × 2F, Z),
34.6 (d, J ) 11.7 Hz, 0.66 × 2F, E), 45.0 (s, 0.66 × 2F), 45.2 (s,
0.34 × 2F), 46.2 (s, 2F), 47.0 (m, 2F), 49.6 (s, 2F); MS m/z
(relative intensity) 416 (M+, 58.99), 415 (70.70), 347 (35.03),
83 (23.34), 69 (38.77), 56 (100.00), 55 (72.04), 41 (57.19); HRMS
calcd for C13H13F13: 416.0809, Found: 416.0821.
(m, 1H), 6.46 (m, 1H); 19F NMR δ 3.90 (t, J ) 10 Hz, 3F), 34.9
(d, J ) 11.5 Hz, 2F), 44.6 (d, J ) 7.4 Hz, 2F), 45.1 (d, J ) 6.7
Hz, 4F), 45.9 (s, 2F), 46.6 (s, 2F), 49.3 (d, J ) 10.5 Hz, 2F);
MS m/z (relative intensity) 490 (M+, 20.60), 471 (55.36), 121
(18.42), 71 (100.00), 69 (21.79); HRMS calcd for C12H7F17O:
490.0225, Found: 490.0224.
4. Gen er a l P r oced u r e for th e Rea ction of 1 w ith 8. A
25 mL three-necked flask, equipped with a water condenser
and a magnetic stirring bar, was charged with zinc powder
(488 mg, 7.5 mmol), nickel dichloride (65 mg, 0.5 mmol), and
triphenylphosphine (530 mg, 2.0 mmol). The flask was filled
with nitrogen and the nitrogen purged solvent DMF (10 mL)
was then added. The mixture was heated to about 100 °C to
form a brown catalyst. A mixture of 1a (1.77 g, 5 mmol) and
8a (810 mg, 7.5 mmol) was added and stirred at this temper-
ature for 8 h. The conversion of 1a was 100%, determined by
19F NMR. After cooled, the precipitate was filtered off and the
product was extracted with ether. The combined extracts were
washed with water and dried over Na2SO4. After removing
ether, the residue was subjected to flash chromatography on
silica gel to give 9a a as a colorless oil (1.32 g, yield 62%).
9a a (o/p/m ) 44:38:18): colorless oil; 1H NMR δ 3.85 (s, 3H),
6.98-7.53 (m, 4H); 19F NMR δ 4.04 (t, J ) 8.5 Hz, 3F), 30.9 (t,
J ) 15 Hz, 0.44 × 2F, o), 32.9 (t, J ) 15 Hz, 0.38 × 2F, p),
33.8 (t, J ) 15 Hz, 0.18 × 2F, m), 44.6 (m, 2F), 45.2 (m, 2F),
46.0 (d, J ) 8 Hz, 2F), 49.4 (s, 2F); MS m/z (relative intensity)
426 (M+, 100.00), 407 (18.60), 219 (8.11), 157 (66.19), 109
(18.21), 69 (3.35); HRMS calcd for C13H7F13O: 426.0289,
Found: 426.0245.
7a c: colorless oil; 1H NMR δ 0.89 (t, J ) 6.5 Hz, 3H), 1.28-
1.86 (m, 12H), 2.19-2.33 (m, 2H), 5.41-6.46 (m, 2H); 19F NMR
δ 3.87 (t, J ) 10 Hz, 3F), 29.7 (d, J ) 12.4 Hz, 0.33 × 2F, Z),
34.3 (d, J ) 11.6 Hz, 0.67 × 2F, E), 44.8 (s, 2F), 46.0 (s, 2F),
46.7 (d, J ) 9.1 Hz, 0.67 × 2F), 46.9 (d, J ) 14.3 Hz, 0.33 ×
2F), 49.3 (s, 2F); MS m/z (relative intensity) 457 (M+ - 1, 3.87),
414 (22.69), 83 (38.89), 70 (72.69), 69 (67.71), 57 (100.00), 56
(94.03), 55 (83.32), 43 (83.88), 41 (68.85); HRMS calcd for
1
9a b: colorless oil; H NMR δ 3.01 (s, 6H), 6.70 (d, J ) 8.9
C
16H19F13: 458.1279, Found: 458.1290.
7a d : colorless oil; H NMR δ 5.42-6.50 (m, 2H), 7.25 (m,
Hz, 2H), 7.40 (d, J ) 8.9 Hz, 2H); 19F NMR δ 4.08 (t, J ) 10
Hz, 3F), 32.4 (t, J ) 14 Hz, 2F), 44.8 (s, 2F), 45.2 (m, 2F), 46.5
(d, J ) 6 Hz, 2F), 49.4 (m, 2F); MS m/z (relative intensity)
439 (M+, 64.21), 420 (15.31), 170 (100.00), 154 (15.42), 69
(6.34); Anal. Calcd for C14H10F13N: C, 38.28; H, 2.29; N, 3.19.
Found: C, 38.23; H, 2.36; N, 3.46.
1
5H); 19F NMR δ 3.96 (t, J ) 9.8 Hz, 3F), 29.8 (d, J ) 13.0 Hz,
0.40 × 2F, Z), 34.4 (d, J ) 11.2 Hz, 0.60 × 2F, E), 44.8 (s, 2F),
46.0 (s, 2F), 46.6 (s, 2F), 49.3 (s, 2F); MS m/z (relative intensity)
422 (M+, 1.62), 339 (42.01), 220 (28.59), 205 (100.00), 145
(19.23), 57 (34.45), 43 (34.32); HRMS calcd for C14H7 F13
422.0340, Found: 422.0383.
:
9a c: colorless oil; 1H NMR δ 3.78 (s, 3H), 3.84 (br, 2H), 6.72
(d, J ) 8.8 Hz, 1H), 6.88-6.98 (m, 2H); 19F NMR δ 4.10 (t, J
) 10 Hz, 3F), 31.8 (t, J ) 14 Hz, 2F), 45.0 (s, 4F), 45.6 (s, 2F),
49.5 (s, 2F); MS m/z (relative intensity) 441 (M+, 100.00), 426
(22.38), 172 (37.82), 157 (3.35), 129 (7.90), 69 (1.45); Anal.
Calcd for C13H8F13NO: C, 35.39; H, 1.83; N, 3.17; F, 55.98.
Found: C, 35.44; H, 1.88; N, 3.35; F, 56.02.
7a e: colorless oil; 1H NMR δ 3.41 (s, 3H), 4.08 (m, 2H),
5.92-6.49 (m, 2H); 19F NMR δ 3.87 (t, J ) 10 Hz, 3F), 34.9 (d,
J ) 11.5 Hz, 2F), 44.8 (s, 2F), 46.0 (s, 2F), 46.6 (s, 2F), 49.4 (s,
2F); MS m/z (relative intensity) 390 (M+, 5.92), 127 (99.40),
69 (28.99), 57 (53.61), 56 (100.00), 55 (47.30), 43 (53.43), 41
(51.05); HRMS calcd for C10H7F13O: 390.0289, Found: 390.0251.
7ba : colorless oil; 1H NMR δ 0.90 (t, J ) 6.2 Hz, 3H), 1.27-
1.64 (m, 6H), 2.16-2.32 (m, 2H), 5.46-6.44 (m, 3H); 19F NMR
δ 29.7 (d, J ) 9.5 Hz, 0.34 × 2F, Z), 34.4 (d, J ) 9.4 Hz, 0.66
× 2F, E), 48.7 (t, J ) 7.6 Hz, 0.66 × 2F), 48.9 (d, J ) 7.1 Hz,
0.34 × 2F), 53.1 (d, J ) 4.8 Hz, 0.66 × 2F), 53.4 (d, J ) 5.5
Hz, 0.34 × 2F), 60.6 (d, J ) 48.6 Hz, 2F); MS m/z (relative
intensity) 298 (M+, 15.79), 270 (18.42), 70 (71.80), 57 (51.13),
56 (100.00), 55 (81.39), 44 (77.44), 43 (53.20), 41 (74.25); HRMS
calcd for C11H14F8: 298.0967, Found: 298.0931.
1
9a d : colorless oil; bp 88-90 °C/20 mmHg; H NMR d 6.31
(d, J ) 1.0 Hz, 1H), 6.63 (s, 1H), 6.95 (s, 1H), 8.53 (br, 1H); 19
F
NMR d 4.02 (t, J ) 9.5 Hz, 3F), 30.42 (t, J ) 13.0 Hz, 2F),
45.0 (s, 2F), 45.8 (d, J ) 13 Hz, 2F), 46.1 (s, 2F), 49.4 (s, 2F).
MS m/z (relative intensity) 386 (M+ + 1, 4.85), 385 (M+, 30.67),
366 (10.16), 347 (14.49), 178 (25.82), 147 (13.19), 116 (100.00),
69 (18.24). Anal. Calcd for C10H4F13N: C, 31.17; H, 1.04; N,
3.64; F, 64.16. Found: C, 31.23; H, 1.26; N, 3.85; F, 64.54.
9a e:40 colorless oil; 1H NMR d 1.44 (s, 3H), 2.25 (s, 3H), 6.60
(d, J ) 4.8 Hz, 1H), 7.43 (d, J ) 5.2 Hz, 1H); 19F NMR d 5.16
(t, J ) 10 Hz, 3F), 37.1 (m, 2F), 43.4 (m, 2F), 45.8 (s, 2F), 46.7
7bb: colorless oil; 1H NMR δ 0.88 (t, J ) 6.8 Hz, 3H), 1.17-
1.68 (m, 10H), 2.15-2.32 (m, 2H), 5.46-6.43 (m, 3H); 19F NMR
δ 29.6 (d, J ) 9.4 Hz, 0.34 × 2F, Z), 34.3 (d, J ) 9.5 Hz, 0.66
× 2F, E), 48.6 (t, J ) 7.8 Hz, 0.66 × 2F), 48.8 (d, J ) 6.7 Hz,
0.34 × 2F), 53.0 (d, J ) 5.9 Hz, 2F), 60.5 (d, J ) 50.3 Hz, 2F);
(40) Huang, W.-Y.; Ma, W.-P. Chin. Chem. Lett. 1991, 2, 755.

4656 J . Org. Chem., Vol. 66, No. 13, 2001
Huang and Chen
(s, 2F), 50.2 (s, 2F). MS m/z (relative intensity) 414 (M+ + 1,
100.00), 412 (M+ - 1, 30.55), 394 (3.34), 95 (12.98), 94 (21.88),
69 (2.05).
9d c: white solid; 1H NMR δ 3.68 (s, 2H), 3.76 (br, 3H), 6.70
(d, J ) 8.8 Hz, 1H), 6.85 (d, J ) 2.9 Hz, 1H), 6.93 (dd, J ) 8.8,
2.9 Hz, 1H); 19F NMR δ 4.04 (t, J ) 10 Hz, 3F), 31.8 (t, J ) 15
Hz, 2F), 44.7 (s, 2F), 45.0 (s, 4F), 45.2 (s, 2F), 46.0 (s, 2F),
49.4 (m, 2F); MS m/z (relative intensity) 542 (M+ + 1, 40.41),
541 (M+, 100.00), 526 (13.11), 172 (21.07), 129 (5.91), 69 (2.42);
Anal. Calcd for C15H8F17NO: C, 33.29; H, 1.49; N, 2.59; F,
59.68. Found: C, 33.46; H, 1.59; N, 2.55; F, 59.92.
1
9bd : colorless oil; H NMR d 5.99 (tt, J ) 52, 5.5 Hz, 1H),
6.31 (m, 1H), 6.63 (s, 1H), 6.96 (d, J ) 1.1 Hz, 1H), 8.50 (br,
1H); 19F NMR d 24.7 (s, 2F), 42.8 (s, 2F), 48.5 (t, J ) 5 Hz,
2F), 56.9 (d, J ) 51.8 Hz, 2F); MS m/z (relative intensity) 267
(M+, 16.23), 248 (3.87), 210 (21.65), 144 (100.00), 116 (75.20),
94 (23.55), 51 (21.42); Anal. Calcd for C8H5F8N: C, 35.97; H,
1.89; N, 5.24; F, 56.90. Found: C, 36.16; H, 1.72; N, 5.50; F,
56.73.
9d d : Colorless oil; bp 112-114 °C/20 mmHg; 1H NMR d
6.36 (s, 1H), 6.65 (s, 1H), 6.97 (s, 1H), 8.50 (br, 1H). 19F NMR
d 0.26 (t, J ) 9.6 Hz, 3F), 24.84 (t, J ) 13.5 Hz, 2F), 40.1 (s,
2F), 40.43 (s, 4F), 40.82 (s, 2F), 41.27 (s, 2F), 44.78 (t, J ) 14
Hz, 2F); MS m/z (relative intensity) 485 (M+, 94.03), 466
(43.83), 447 (17.26), 409 (56.1), 178 (22.04), 116 (100.00), 69
(12.43); Anal. Calcd for C12H4F17N: C, 29.69; H, 0.82; N, 2.87;
F, 66.60. Found: C, 29.52; H, 1.00; N, 2.93; F, 66.41.
9be: colorless oil; 1H NMR d1.43 (s, 3H), 2.23 (s, 3H), 6.60
(d, J ) 4.8 Hz, 1H), 6.67 (tt, J ) 51.2, 5.8 Hz, 1H), 7.44 (d, J
) 4.8 Hz, 1H); 19F NMR d 31.9 (m, 2F), 40.1 (m, 2F), 48.8 (m,
2F), 57.0 (d, J ) 51 Hz, 2F); MS m/z (relative intensity) 295
(M+, 11.74), 294 (18.41), 269 (17.73), 144 (100.00), 118 (78.68),
95 (67.24), 51 (21.02); HRMS calcd for C10H9F8N: 295.0607,
Found: 295.0616.
9d e: colorless oil; 1H NMR d 1.44 (s, 3H), 2.26 (s, 3H), 6.63
(d, J ) 4.8 Hz, 1H), 7.46 (d, J ) 4.8 Hz, 1H); 19F NMR d -0.47
(t, J ) 9.8 Hz, 3F), 31.6 (m, 2F), 38.0 (m, 2F), 40.4 (s, 2F),
40.4 (s, 4F), 41.3 (s, 2F), 44.8 (s, 2F); MS m/z (relative intensity)
513 (M+, 100.00), 494 (44.46), 444 (7.01), 325 (3.51), 144
(21.52); Anal. Calcd for C14H8F17N: C, 32.77; H, 1.57; N, 2.73;
F, 62.93. Found: C, 32.70; H, 1.78; N, 2.75; F, 62.60.
9d a (o/p/m ) 48:32:20): colorless oil; 1H NMR δ 3.86 (s, 3H),
6.98-7.54 (m, 4H); 19F NMR δ 4.10 (t, J ) 10 Hz, 3F), 30.9 (t,
J ) 13 Hz, 0.48 × 2F, o), 32.9 (t, J ) 15 Hz, 0.32 × 2F, p),
33.8 (t, J ) 15 Hz, 0.20 × 2F, m), 44.5 (m, 2F), 45.1 (m, 6F),
46.0 (s, 2F), 49.4 (t, J ) 11 Hz, 2F); MS m/z (relative intensity)
526 (M+, 67.28), 507 (26.43), 219 (7.74), 157 (100.00), 109
(15.71), 69 (4.26); Anal. Calcd for C15H7F17O: C, 34.24; H, 1.34;
F, 61.38. Found: C, 34.29; H, 1.31; F, 61.25.
Ack n ow led gm en t. We thank the Natural Science
Foundation of China for support of this work.
1
9d b: white solid; H NMR δ 3.03 (s, 6H), 6.72 (d, J ) 9.0
Hz, 2H), 7.41 (d, J ) 9.0 Hz, 2H); 19F NMR δ 3.98 (t, J ) 10
Hz, 3F), 32.4 (t, J ) 15 Hz, 2F), 44.5 (s, 2F), 45.2 (s, 6F), 45.9
(s, 2F), 49.3 (t, J ) 14 Hz, 2F); MS m/z (relative intensity)
539 (M+, 52.21), 520 (16.87), 170 (100.00), 154 (12.82), 119
(2.91), 69 (6.13); Anal. Calcd for C16H10F17N: C, 35.64; H, 1.87;
N, 2.60; F, 59.89. Found: C, 35.46; H, 1.98; N, 3.08; F, 59.40.
Su p p or tin g In for m a tion Ava ila ble: 1H NMR and 19F
NMR spectra of 3a a , 3a c, 3ca , 5a b, 5bb, 5ca , 7a c, 7d e, 9a a ,
9a d , 9a e, 9d b, and 9d c. This material is available free of
charge via the Internet at http://pubs.acs.org.
J O010178J