A convenient preparation of 3,3,3-trifluoro-1-propynylamines and their Lewis acid catalyzed reaction with carbonyl compounds leading to (Z)-α-(trifluoromethyl)-α,β-unsaturated amides

Article abstract of DOI:10.1021/jo001760v

N,N-Dialkyl(3,3,3-trifluoro-1-propynyl)amines were readily prepared by a three-step procedure starting from commercially available 2,2,3,3,3-pentafluoropropanol. These fluorinated alkynylamines reacted smoothly with a variety of aldehydes or ketones in the presence of a catalytic amount of Lewis acid and molecular sieves 4A at ambient temperature to produce the corresponding α(trifluoromethyl)-α,β-unsaturated amides in good to excellent yields with high Z-stereoselectivity.

Full text of DOI:10.1021/jo001760v

3442
J . Org. Chem. 2001, 66, 3442-3448
A Con ven ien t P r ep a r a tion of 3,3,3-Tr iflu or o-1-p r op yn yla m in es a n d
Th eir Lew is Acid Ca ta lyzed Rea ction w ith Ca r bon yl Com p ou n d s
Lea d in g to (Z)-r-(Tr iflu or om eth yl)-r,â-u n sa tu r a ted Am id es1
Toshiya Mantani, Keisuke Shiomi, Tsutomu Konno, Takashi Ishihara,* and Hiroki Yamanaka
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki,
Sakyo-ku, Kyoto 606-8585, J apan
ishihara@ipc.kit.ac.jp
Received December 18, 2000
N,N-Dialkyl(3,3,3-trifluoro-1-propynyl)amines were readily prepared by a three-step procedure
starting from commercially available 2,2,3,3,3-pentafluoropropanol. These fluorinated alkynylamines
reacted smoothly with a variety of aldehydes or ketones in the presence of a catalytic amount of
Lewis acid and molecular sieves 4Å at ambient temperature to produce the corresponding
R-(trifluoromethyl)-R,â-unsaturated amides in good to excellent yields with high Z-stereoselectivity.
In tr od u ction
ever, suffer from serious drawbacks, such as an extremely
limited scope of the reaction, lack of stereoselectivity, and/
or difficulty in the availability of the starting propanoate.
Therefore, there is a great need to develop a more
convenient and effective means for the synthesis of such
R-trifluoromethylated compounds.
In close connection with our continuing studies on the
preparations and applications of polyfluoroalkyl- or
alkenylamines,11,12 we recently directed our attention to
fluorinated 1-alkynylamines, which should be expected
to serve as useful building blocks for preparing fluori-
nated organic compounds, since ordinary 1-alkynyl-
amines or ynamines are recognized to have unique and
versatile reactivities and thereby to undergo various
types of organic reactions,13-17 for example, the hetero
R,â-Unsaturated carbonyl compounds have widely been
utilized as potent synthetic blocks in organic synthesis,
particularly as Michael acceptors for conjugate addition
reactions2 or dienophiles and dipolarophiles for cyclo-
addition reactions.3-5 The counterparts carrying the
trifluoromethyl substituent at the R position are likewise
of great synthetic value as synthons for the construction
of a variety of selectively trifluoromethylated compounds,
which attract much attention in biological or material
chemistry.6 To our knowledge, only three kinds of
methods appear in the literature for the preparation
of R-(trifluoromethyl)-R,â-unsaturated carbonyl com-
pounds; the pyrolysis of the O-acetate of trifluoroacetone
cyanohydrin or R-hydroxy-R-(trifluoromethyl)propanoate,7
the direct or Pd(II)-catalyzed carbonylation of 3,3,3-
trifluoro-1-propen-2-yllithium derived from 2-bromo-3,3,3-
trifluoro-1-propene,8,9 and the Reformatsky reaction of
2,2-dichloro-3,3,3-trifluoropropanoate with aldehydes fol-
lowed by reductive elimination.10 These methods, how-
(11) (a) Yamanaka, H.; Kuwabara, M.; Komori, M.; Otani, M.; Kase,
K.; Fukunishi, K.; Nomura, M. Nippon Kagaku Kaishi 1983, 112. (b)
Yamanaka, H.; Kuwabara, M.; Komori, M.; Otani, M.; Fukunishi, K.;
Nomura, M. Nippon Kagaku Kaishi 1984, 598. (c) Yamanaka, H.;
Kuwabara, M.; Okudo, M.; Fukunishi, K.; Nomura, M. Nippon Kagaku
Kaishi 1985, 1988. (d) Yamanaka, H.; Ganbayashi, H.; Kuwabara, M.;
Fukunishi, K.; Nomura, M. Nippon Kagaku Kaishi 1988, 1036.
(12) Yamanaka, H.; Yamashita, S.; Ishihara, T. Tetrahedron Lett.
1992, 33, 357. Yamanaka, H.; Yamashta, S.; Ishihara, T. Synlett 1993,
353. Yamanaka, H.; Shiomi, K.; Ishihara, T. Tetrahedron Lett. 1995,
36, 7267.
(13) For selected reviews, see: Viehe, H. G. Angew. Chem. Int. Ed.
Engl. 1967, 6, 767. Ficini, J . Tetrahedron 1976, 32, 1449. Collard-
Motte, J .; J anousek, Z. Top. Curr. Chem. 1986, 130, 89.
(14) For the hetero Diels-Alder reactions, see: (a) Ficini, J .; Krief,
A. Tetrahedron Lett. 1969, 1427. (b) Ficini, J .; Krief, A. Tetrahedron
Lett. 1970, 885. (c) Ficini, J .; Besseyre, J .; Krief, A. Bull. Soc. Chim.
Fr. 1976, 987. (d) Myers, P. L.; Lewis, J . W. J . Heterocycl. Chem. 1973,
10, 165. (e) Steinhagen, H.; Corey, E. J . Angew. Chem., Int. Ed. 1999,
38, 1928.
(15) For other cycloaddition reactions, see: Nesi, R.; Giomi, D.;
Papaleo, S.; Bracci, S. J . Org. Chem. 1989, 54, 706. Nesi, R.; Giomi,
D.; Papaleo, S.; Turchi, S. Tetrahedron Lett. 1991, 32, 6223. Sakai,
N.; Funabashi, M.; Hamada, T.; Minakata, S.; Kamatsu, M. Tetrahe-
dron 1999, 55, 13703. Nesi, R.; Turchi, S.; Giomi, D.; Danesi, A.
Tetrahedron 1999, 55, 13809. Balsells, J .; Vazquez, J .; Mayano, A.;
Pericas, M. A.; Riera, A. J . Org. Chem. 2000, 65, 7291.
(16) For the reactions with carbonyl compounds, see: Guillaume,
M.; J anousek, Z.; Viehe, H. G. Synthesis 1995, 920. Wentrup, C.; Rao,
V. V. R.; Frank, W.; Fulloon, B. E.; Moloney, D. W. J .; Mosandl, T. J .
Org. Chem. 1999, 64, 3608. Rainier, J . D.; Imbriglio, J . E. J . Org. Chem.
2000, 65, 7272.
(1) Based in part on the thesis of T. Mantani, Kyoto Institute of
Technology, 2001. A portion of this work has been reported in a
preliminary form: Mantani, T.; Shiomi, K.; Ishihara, T.; Yamanaka,
H. Chem. Lett. 1999, 855.
(2) For selected reviews on the conjugate addition reactions, see:
Posner, G. H. Org. React. 1972, 19, 1. Lipshutz, B. H.; Sengupta, S.
Org. React. 1992, 41, 135. Davies, S. G.; Ichihara, O. J . Synth. Org.
Chem. J pn. 1997, 55, 26.
(3) Carruthers, W. Cycloaddition Reactions in Organic Synthesis;
Pergamon Press: Oxford, 1990.
(4) For selected reviews on the Diels-Alder reactions, see: Holmes,
H. L. Org. React. 1948, 4, 60. Ciganek, E. Org. React. 1984, 32, 1.
(5) Padwa, A. 1,3-Dipolar Cycloaddition Chemistry; J ohn Wiley &
Sons: New York, 1984; Vols. I and II. For a review on the 1,3-dipolar
cycloaddition reactions, see: Confalone, P. N.; Huie, E. M. Org. React.
1988, 36, 1.
(6) Welch, J . T.; Eswarakrishnan, S. Fluorine in Bioorganic Chem-
istry; Wiley-Interscience: New York, 1991. Biomedical Frontiers of
Fluorine Chemistry; Ojima, I., McCarthy, J . R., Welch, J . T., Eds.;
American Chemical Society: Washington, DC, 1996; Vol. 639. Enan-
tiocontrolled Synthesis of Fluoro-Organic Compounds; Soloshonok, V.
A. Ed.; J ohn Wiley & Sons: Chichester, 1999.
(7) Buxton, M. W.; Stacey, M.; Tatlow, J . C. J . Chem. Soc. C 1954,
366.
(8) Drakesmith, F. G.; Stewart, O. J .; Tarrant, P. J . Org. Chem.
1967, 33, 280.
(9) Fuchikami, T.; Yamanouchi, A.; Ojima, I. Synthesis 1984, 766.
(10) Allmendinger, T.; Lang, R. W. Tetrahedron Lett. 1991, 32, 339.
(17) For the reactions with allylic alcohols or acids, see: (a) Wolf,
V.; Kowitz, F. J ustus Liebigs Ann. Chem. 1960, 638, 33. (b) Ficini, J .;
Barbara, C. Tetrahedron Lett. 1966, 6425. (c) Ficini, J .; Lumbroso-
Bader, N.; Pouliquen, J . Tetrahedron Lett. 1968, 4139.
10.1021/jo001760v CCC: $20.00 © 2001 American Chemical Society
Published on Web 04/21/2001

3,3,3-Trifluoro-1-propynylamines
J . Org. Chem., Vol. 66, No. 10, 2001 3443
Sch em e 1a
Sch em e 2
Ta ble 2. P r ep a r a tion of Yn a m in es 2 fr om Ter tia r y
Am in es 1
temp time
yielda
recovery
entry
1
base
additive (°C) (h)
of 2 (%)
of 1 (%)
1
2
3
4
5
6
7
8
9
1A LDA
1A LDA
1A LDA
1A LDA
1A LDA
1A BuLi
none
none
none
DMPU
DMPU
none
0
2
2
2A, 14
2A, 47
75
41
24
9
a
Key: (a) 2-nitrobenzenesulfonyl chloride, NaOH/H2O, 60 °C,
rt
rt
0
rt
rt
rt
0
rt
rt
rt
2 h. (b) (CF3SO2)2O, neat, reflux, 3 h. (c) Method A; R2NH or
BnNMe2, neat, 140-160 °C. (d) Method B; R2NH, neat.
24 2A, 66
2
2
2
2A, 84
2A, 94(75)
2A, 5
tr
Ta ble 1. P r ep a r a tion of
N,N-Dia lk yl(2,2,3,3,3-p en ta flu or op r op yl)a m in es 1
43
44
tr
tr
21
100
1A t-BuOK none
24 2A, 23b
temp
(°C)
time
(h)
yieldb
of 1 (%)
1B LDA
1C LDA
1D LDA
1E LDA
DMPU
2
2
2B, 92
2C, 97
entry
amine
methoda
DMPU
DMPU
DMPU
10
11
24 2D, 66
24 2E, 0
1
2
3
4
5
6
7
Bu2NH
Bu2NH
A
B
A
A
B
B
B
150-160
60
150-160
140-150
rt
6
1
4
6
1
1A, 48
1A, 93
1B, 86
1C, tr
1C, 79
1D, 45
1E, 49
a
BnNMe2
piperidine
piperidine
i-Pr2NH
Bn2NH
Determined by 19F NMR. Value in parentheses is of isolated
yield. b N,N-Dibutyl(2,3,3,3-tetrafluoro-1-propenyl)amine was also
formed in 33% yield.
reflux
reflux
24
24
tions using o-nitrobenzenesulfonate (entry 4) and tri-
fluoromethanesulfonate (entry 5). These trends in the
yields of 1 can be considered to result primarily from the
difference in reactivity between the two sulfonates.
Triflate has a far superior leaving ability. It should be
noted that the Hofmann-like degradation between o-
nitrobenzenesulfonate and an excess amount (3 equiv)
of N,N-dimethylbenzylamine at high temperatures was
strongly recommended for preparing N,N-dimethyl-
(2,2,3,3,3-pentafluoropropyl)amine (1B) (entry 3).11c N,N-
diisopropyl- (1D) and N,N-dibenzyl(2,2,3,3,3-pentafluoro-
propyl)amine (1E) were also obtained in moderate yields
by the reaction using trifluoromethanesulfonate (entries
6 and 7).
On reaction with base, these fluorinated tertiary
amines 1 underwent dehydrofluorination to the desired
ynamines 2 (Scheme 2). As summarized in Table 2,
treatment of 1A with 2.2 equiv of lithium diisopropyl-
amide (LDA) in tetrahydrofuran (THF) at 0 °C for 2 h
provided the ynamine 2A in only 14% yield, while 75%
of the starting amine 1A was recovered (entry 1). The
reaction at room temperature and/or for a prolonged
reaction time led to an increase in the yields of 2A
(entries 2 and 3). The use of 2.2 equiv of 1,3-dimethyl-
3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) as an
additive was found to allow the reaction to proceed quite
efficiently (entries 4 and 5). Thus, the reaction of 1A with
LDA (2.2 equiv) in THF containing DMPU (2.2 equiv) at
room temperature for 2 h afforded the ynamine 2A in
94% yield. Bases other than LDA, such as butyllithium
and potassium tert-butoxide, were not as effective for the
reaction (entries 6 and 7). Similarly, N,N-dialkyl(3,3,3-
trifluoropropynyl)amines 2B-D were prepared through
the reactions of 1B-D with LDA in THF and DMPU at
0 °C or room temperature, as shown in entries 8-10.
However, no ynamine 2E could be obtained. The reaction
of 1E with LDA resulted in a quantitative recovery of
the starting amine (entry 11).
a
See the keys (c) and (d) in Scheme 1 as well as the Experi-
b
mental Section. Isolated yields based on the sulfonates.
Diels-Alder reaction with R,â-unsaturated ketones af-
fording γ-pyrane derivatives14a-d or the reaction with
allylic alcohols leading to γ,δ-unsaturated amines.17a,b
Despite such attractive utility, there are few reports
dealing with the preparation and reactions of fluorine-
containing ynamines.18 In this paper we disclose the first
expedient preparation of trifluoromethylated ynamines,
N,N-dialkyl(3,3,3-trifluoro-1-propynyl)amines (2) and their
Lewis acid catalyzed reactions with carbonyl compounds,
demonstrating that these reactions provide us with a
highly efficient and general method for the stereoselective
synthesis of R-(trifluoromethyl)-R,â-unsaturated amides
3.
Resu lts a n d Discu ssion
P r ep a r a tion of Tr iflu or om eth yla ted Yn a m in es 2.
As the precursors of trifluoromethylated ynamines, N,N-
dialkyl(2,2,3,3,3-pentafluoropropyl)amines (1) were pre-
pared from commercially available 2,2,3,3,3-penta-
fluoropropanol, which was converted into the correspond-
ing sulfonate esters either by the reaction with o-
nitrobenzenesulfonyl chloride and sodium hydroxide in
water at 60 °C for 2 h11a or by the reaction with
trifluoromethanesulfonic anhydride at reflux tempera-
ture for 3 h.19 The obtained o-nitrobenzenesulfonate and
trifluoromethanesulfonate (triflate) were subjected to a
Hofmann-like degradation with N,N-dimethylbenzyl-
amine11c or polyfluoroalkylation of a secondary amine, as
shown in Scheme 1. The results of the reactions con-
ducted under various conditions are summarized in Table
1. The reaction of o-nitrobenzenesulfonate with dibutyl-
amine gave N,N-dibutyl(2,2,3,3,3-pentafluoropropyl)-
amine (1A) in appreciably lower yield than the reaction
using trifluoromethanesulfonate (entries 1 and 2). A
similar trend was observed in the preparation of N-(2,2,3,
3,3-pentafluoropropyl)piperidine (1C) through the reac-
Reaction of Tr iflu or om eth ylated Yn am in es 2 with
Ca r bon yl Com p ou n d s. First, the reactions of 2A with
benzaldehyde (Scheme 3) were examined under various
conditions, as shown in Table 3. Thus, 2A and benzalde-
hyde in CH2Cl2 in the presence of molecular sieves 4Å
(MS 4Å) showed little evidence of reaction. Acidic workup
(18) Freear, J .; Tipping, A. E. J . Chem. Soc. C 1968, 1096.
(19) Hanzen, R. L. J . Org. Chem. 1965, 30, 4322.

3444 J . Org. Chem., Vol. 66, No. 10, 2001
Mantani et al.
Sch em e 3
Sch em e 4
Ta ble 3. Scr een in g of Rea ction Con d ition s for th e
Rea ction of Yn a m in es 2 w ith Ben za ld eh yd e
Ta ble 4. Syn th esis of r,â-Un sa tu r a ted Am id es 3A by th e
Rea ction of Yn a m in es 2A w ith Ca r bon yl Com p ou n d s
time
(h)
yieldb
of 3 (%) of 4 (%)
yieldb
isomer
time yielda of
R2 (h)
3A (%) of 3A (Z:E) 4A (%)
ratiob
yielda of
entry
2
Lewis acida solvent
entry
R1
1
2
2A none
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
PhCH3
Et2O
24
1
1
24
1
1
1
1
1
1
3Aa , 3
79
tr
66
8
5
12
5
3
6
7
2A BF3‚OEt2
3Aa , 92
3Aa , 28
3Aa , 71
3Aa , 90
3Aa , 80
3Aa , 81
3Aa , 84
3Aa , 82
3Aa , 82
3Ba , 65
3Ca , 73
3Da , 40
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Ph
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
Et
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
3Aa , 92
3Ab, 95
3Ac, 81
3Ad , 92
3Ae, 87
3Af, 97
3Ag, 94
3Ah , 82
3Ai, 97
3Aj, 95
3Ak , 88
3Al, 83
3Am , 75
3An , 89
3Ao, 82
3Ap , 68
3Aq, 85
3Ar , 77
3As, 77
3At, 72
>97:<3
>97:<3
>97:<3
>97:<3
>97:<3
96:4
>97:<3
>97:<3
>97:<3
96:4
>97:<3
>97:<3
>97:<3
96:4
>97:<3
56:44
tr
2
6
4
8
tr
tr
tr
tr
3
tr
5
20
3
3c
4c
5
2A BF3‚OEt2
p-MeC6H4
p-MeOC6H4
p-ClC6H4
1-naphthyl
2-thienyl
2-furyl
(E)-PhCHdCH
(Z)-PhCHdCF
(E)-MeCHdCH
CH2dC(Me)
n-Pr
d
2A La(OTf)3
2A ZnBr2
2A TiCl4
2A SnCl4
2A BF3‚OEt2
2A BF3‚OEt2
2A BF3‚OEt2
2B La(OTf)3
2C La(OTf)3
6
7
8
9
10
11c
12c
13
THF
d
CH2Cl2
CH2Cl2
CH2Cl2
24
24
1
20
18
43
d
2D BF3‚OEt2
n-Hex
i-Pr
c-Hex
a
10 mol % of Lewis acid was used, unless otherwise noted.
Isolated yields. c Without MS 4Å. Employed 30 mol % of
b
d
11
23
6
11
8
La(OTf)3.
16c t-Bu
17
18
19
20
Me
Et
of this mixture gave N,N-dibutyl-3,3,3-trifluoropropan-
amide (4A) in 79% yield, together with 3% of R-(trifluoro-
methyl)-R,â-unsaturated amide 3Aa (entry 1). When 10
mol % of boron trifluoride etherate (BF3‚OEt2) was
employed as a Lewis acid, the reaction was markedly
facilitated to give the desired amide 3Aa in high yield
(entry 2). This amide 3Aa was an isomeric mixture with
Z:E of >97:<3. The presence of MS 4Å was requisite to
suppress the formation of 4A, which may result from the
acidic hydration with a slight amount of water contami-
nating the starting ynamine 2A. In fact, 19F NMR
analysis for the reaction conducted in the absence of MS
4Å clearly indicated the in situ formation of 4A as well
as 3Aa , which were obtained in 66% and 28% yield,
respectively, after a usual workup (entry 3). The reaction
using lanthanum(III) triflate, known to be resistant to
hydrolysis,20 gave a satisfactory result even in the
absence of MS 4Å, though the reaction time had to be
extended to 24 h (entry 4). Other Lewis acids, such as
zinc bromide, titanium(IV) chloride, and tin(IV) chloride,
were also effective for the reaction (entries 5-7). Toluene,
diethyl ether, and THF could be utilized as solvents
comparable to CH2Cl2 (entries 8-10). The reactions
between 2B or 2C and benzaldehyde in the presence of
La(OTf)3 (30 mol %) provided the corresponding R,â-
unsaturated amides 3Ba and 3Ca in good yields with
high Z-stereoselectivity (entries 11 and 12). On the other
hand, the ynamine 2D reacted reluctantly with benz-
aldehyde in the presence of BF3‚OEt2, leading to the
amide 3Da in 40% yield (entry 13). Probably, bulky
isopropyl groups on the amine nitrogen are responsible
in part for such low efficiency of the reaction.
-(CH2)5-
Ph
Me
71:29
9
Isolated yields. Measured by 19F NMR before isolation.
a
b
c Carried out by using 20 mol % of BF3‚OEt2.
results are summarized in Table 4. Thus, when various
types of aldehydes, such as aromatic, heteroaromatic, R,â-
unsaturated, and aliphatic aldehydes, were allowed to
react with 2A under the influence of 10 mol % of BF3‚
OEt2 and MS 4Å in CH2Cl2 at ambient temperature for
1 h, the corresponding R-(trifluoromethyl)-R,â-unsatur-
ated amides 3A were provided in good to excellent yields.
More significantly, these reactions of aldehydes, except
2,2-dimethylpropanal, took place with very high levels
of stereoselectivity to produce the (Z)-isomers predomi-
nantly (entries 1-15). The reaction of 2,2-dimethylpro-
panal needed 20 mol % of BF3‚OEt2 and a prolonged
reaction period and gave rise to 68% yield of the amide
3Ap consisting of the two geometrical isomers in a Z:E
ratio of 56:44 (entry 16). A variety of ketones, such as
acetone, 3-pentanone, cyclohexanone, and acetophenone,
were also found to participate nicely in the reaction with
2A, leading to the corresponding R,â-unsaturated amides
3Aq-3At in good yields, as shown in entries 17-20. All
of the reactions using ketones required a longer reaction
time of 2 h for satisfactory results. The reaction of
acetophenone occurred in an appreciably low stereo-
selective manner to result with the formation of 3At as
an isomeric mixture of Z:E ) 71:29 (entry 20)
The geometry of R,â-unsaturated amides 3A was
determined as follows. The 19F NMR spectrum of the
crude amide 3Ba (isomer ratio, 97:3) showed two reso-
nance peaks due to the trifluoromethyl group at -57.74
and -64.81 ppm for the major and minor isomers,
respectively. Since crystallographic analysis of the major
isomer of 3Ba 21 permitted the straightforward assign-
ment of its Z-geometry, the former peak (at lower field)
On the basis of these examinations, the reactions of
2A with other aldehydes or ketones were undertaken by
employing BF3‚OEt2 and CH2Cl2 solvent (Scheme 4). The
(20) For
a review on lanthanide triflates, see: Kobayashi, S.;
Hachiya, I. J . Synth. Org. Chem. J pn. 1995, 53, 370.

3,3,3-Trifluoro-1-propynylamines
J . Org. Chem., Vol. 66, No. 10, 2001 3445
form-d (CDCl3) solution with tetramethylsilane (Me4Si) as an
internal reference. 13C NMR spectra were recorded on a
General Electric QE-300 (75.61 MHz) and/or Bruker DRX-500
(125.75 MHz) NMR spectrometer in a CDCl3 solution with Me4-
Si as an internal standard. A J EOL J NM-EX90A (84.21 MHz)
FT-NMR spectrometer was used for determining 19F NMR
spectra in a CDCl3 solution with the internal standard of
trichlorofluoromethane. Mass (MS) and high-resolution mass
spectra (HRMS) were taken on a Hitachi M-80B or J EOL J MS-
700 mass spectrometer by electron impact (EI) or chemical
ionization (CI) method. Elemental analyses were conducted
with a Yanaco CHN corder MT-5 instrument. Thin-layer
chromatography (TLC) was done on glass plates coated with
silica gel (Merck 60 F254), and column chromatography was
carried out using silica gel (Wakogel C-200) as absorbent.
Tetrahydrofuran (THF) and diethyl ether were freshly
distilled from sodium/benzophenone ketyl under argon. Other
solvents were dried according to the conventional methods
before use. Butyllithium (a 1.6 M hexane solution) was
commercially available from Aldrich or Kanto Chemical Co.
Aldehydes and ketones were distilled (or vacuum distilled) over
calcium hydride or recrystallized from appropriate solvents
and were stored under argon. All chemicals were of reagent
grade and, if necessary, were purified in the usual manner
prior to use. 2,2,3,3,3-Pentafluoropropyl o-nitrobenzene-
sulfonate and trifluoromethanesulfonate were prepared ac-
cording to the literature method11a or slightly modified proce-
dure.19
Typ ica l P r oced u r e for th e P r ep a r a tion of Ter tia r y
Am in es 1. Meth od A.11c A mixture of o-nitrobenzenesulfonate
(50.27 g, 150 mmol) and N,N-dimethylbenzylamine (60.84 g,
450 mmol) was heated with stirring at such temperatures
(140-160 °C) that tertiary amine 1B formed in situ was
constantly distilled. The collected distillate was subjected to
fractional distillation giving the desired amine 1B (86%).
Meth od B. A mixture of trifluoromethanesulfonate (42.32 g,
150 mmol) and dibutylamine (58.16 g, 450 mmol) was stirred
without solvent at 60 °C for 1 h. After cooling to room
temperature, the mixture was filtered to remove dibutyl-
ammonium salt, which was washed with ether (ca. 50 mL).
The filtrate was washed successively with 5% HCl (100 mL ×
2) and with water (50 mL), followed by drying over anhydrous
Na2SO4, filtration, and concentration. The resultant oil was
distilled to yield 1A (93%).
Sch em e 5
corresponding to the major isomer could be distinctly
assigned to the (Z)-isomer and the latter (at higher field)
to the (E)-isomer. These results served to assign the
stereochemistry of other amides 3A. In 19F NMR spectra
of the crude amides 3Aa -3Ap , their major isomers
exhibited the resonance peaks around -54 to -60 ppm,
whereas the minor isomers showed the peaks at consis-
tently higher fields of 5-8 ppm than the major ones. Such
a tendency for the resonances of the two isomers enabled
us to make their geometrical assignments; the isomer
having a lower fluorine chemical shift was determined
as the (Z)-isomer and the isomer possessing a higher
chemical shift as E.
The reactions leading to the amides 3 are presumed
to occur via the mechanism depicted in Scheme 5,
essentially similar to that proposed recently for the
reaction between alkynolates and carbonyl compounds.22a,c
Thus, the ynamine 2 may attack a carbonyl compound
activated by a Lewis acid23 to form an oxetene intermedi-
ate. This intermediate would be subject to conrotatory
ring opening in such a way, designated with the arrow a
in Scheme 5, that the Lewis acid part (L.A.) and the
substituent R1 or R2 (R1 > R2) exert their mutual
repulsive interaction minimally, resulting in the prefer-
ential formation of the (Z)-isomers of the products 3.
In conclusion, we have demonstrated that trifluoro-
methylated ynamines 2, prepared in three steps from
readily available 2,2,3,3,3-pentafluoropropanol, efficiently
undergo Lewis acid catalyzed reactions with a variety of
carbonyl compounds to give predominantly the (Z)-
isomers of the corresponding R-(trifluoromethyl)-R,â-
unsaturated amides 3 in high yields. This reaction will
serve as a convenient and efficient means for the stereo-
selective synthesis of such compounds 3 that are other-
wise difficult to prepare.
N,N-Dibu tyl(2,2,3,3,3-p en ta flu or op r op yl)a m in e (1A):
1
bp 75.0-76.0 °C/20 Torr; IR (film) 2960, 1190, 1110 cm-1; H
NMR (200 MHz) δ 0.91 (t, J ) 7.1 Hz, 6H), 1.22-1.49 (m, 8H),
2.57 (t, J ) 7.1 Hz, 4H), 3.03 (tq, J ) 15.8, 1.1 Hz, 2H); 13C
NMR (125.75 MHz) δ 13.91, 20.23, 29.38, 53.63 (t, J ) 21.8
Hz), 55.16, 115.03 (tq, J ) 253.9, 35.6 Hz), 119.23 (tq, J )
35.6, 286.7 Hz); 19F NMR (84.21 MHz) δ -117.83 (t, J ) 15.8
Hz, 2F), -82.17 (t, J ) 1.1 Hz, 3F); MS (EI) m/z (rel intensity)
261 (M+, 6), 218 (100); HRMS (EI) calcd for C11H20F5N (M+)
261.1516, found 261.1515. Anal. Calcd for C11H20F5N: C, 50.57;
H, 7.72; N, 5.36. Found: C, 49.94; H, 7.62; N, 5.41.
Exp er im en ta l Section
N,N-Dim eth yl(2,2,3,3,3-p en ta flu or op r op yl)a m in e (1B):
Gen er a l Meth od s. Melting points were obtained on a
Shimadzu MM-2 micro melting point determination apparatus
and are uncorrected. Infrared spectra (IR) were taken on a
Shimadzu IR-400 and/or FTIR-8200(PC) spectrophotometer as
film on a NaCl plate or as KBr pellet. H NMR spectra were
measured with a Varian Gemini-200, General Electric QE-
300, and/or Bruker DRX-500 NMR spectrometer in a chloro-
bp 58.0 °C; IR (film) 2960, 1200, 1105 cm-1 1H NMR (200
;
MHz) δ 2.41 (s, 6H), 2.93 (tq, J ) 15.6, 1.1 Hz, 2H); 13C NMR
(125.75 MHz) δ 46.46, 57.76 (t, J ) 22.3 Hz), 114.96 (tq, J )
254.1, 35.8 Hz), 119.12 (tq, J ) 35.8, 285.6 Hz); 19F NMR (84.21
MHz) δ -117.30 (t, J ) 15.6 Hz, 2F), -82.23 (t, J ) 1.1 Hz
3F); MS (EI) m/z (rel intensity) 177 (M+, 100); HRMS (EI) calcd
for C5H8F5N (M+) 177.0577, found 177.0573.
1
N-(2,2,3,3,3-P en t a flu or op r op yl)p ip er id in e (1C): bp
122.0-123.0 °C; IR (film) 2941, 1198, 1134 cm-1; 1H NMR (300
MHz) δ 1.38-1.46 (m, 2H), 1.55-1.463 (m, 4H), 2.58 (t, J )
5.3 Hz, 4H), 2.91 (tq, J ) 15.6, 1.2 Hz, 2H); 13C NMR (125.75
MHz) δ 23.70, 25.97, 55.66, 57.44 (t, J ) 22.0 Hz), 114.92 (tq,
J ) 290.1, 35.6 Hz), 119.06 (tq, J ) 35.6, 286.2 Hz); 19F NMR
(84.21 MHz) δ -119.51 (t, J ) 15.6 Hz, 2F), -84.54 (t, J ) 1.2
Hz, 3F); MS (EI) m/z (rel intensity) 217 (M+, 19), 98 (100);
HRMS (EI) calcd for C8H12F5N (M+) 217.0870, found 217.0894.
N,N-Diisop r op yl(2,2,3,3,3-p en t a flu or op r op yl)a m in e
(1D): bp 136.0-136.5 °C; IR (film) 2972, 1194, 1153 cm-1; 1H
NMR (300 MHz) δ 1.02 (d, J ) 6.5 Hz, 12H), 2.99-3.11 (m,
(21) For details regarding the X-ray crystal structure of 3Ba , see
the Supporting Information.
(22) Shindo et al. have recently proposed the mechanism for the [2
+ 2] cycloaddition reactions of alkynolates with carbonyl and related
compounds; see: (a) Shindo, M.; Sato, Y.; Shishido, K. Tetrahedron
Lett. 1998, 39, 4857. (b) Shindo, M.; Sato, Y.; Shishido, K. J . Am. Chem.
Soc. 1999, 121, 6507. (c) Shindo, M.; Sato, Y.; Shishido, K. J . Org.
Chem. 2000, 65, 5443. (d) Shindo, M.; Oya, S.; Murakami, R.; Sato,
Y.; Shishido, K. Tetrahedron Lett. 2000, 41, 5947.
(23) Taking into account the highly electronegative nature of the
trifluoromethyl goup, one can assume that as basicity of the ynamine
2 is reduced definitely by its electronic effect, the carbonyl compound
may participate effectively in coordination with Lewis acid.

3446 J . Org. Chem., Vol. 66, No. 10, 2001
Mantani et al.
4H); 13C NMR (125.75 MHz) δ 20.80, 45.44 (t, J ) 22.3 Hz),
49.50, 114.73 (tq, J ) 252.1, 35.5 Hz), 119.55 (tq, J ) 35.5,
286.5 Hz); 19F NMR (84.21 MHz) δ -120.35 (t, J ) 15.6 Hz,
2F), -84.43 (s, 3F); MS (EI) m/z (rel intensity) 233 (M+, 2),
176 (100); HRMS (EI) calcd for C9H16F5N (M+) 233.2102, found
233.1207.
N,N-Diben zyl(2,2,3,3,3-p en ta flu or op r op yl)a m in e (1E):
bp 149.0 °C/3 Torr; IR (film) 3030, 1196, 1130 cm-1; 1H NMR
(300 MHz) δ 3.11 (tq, J ) 15.6, 0.9 Hz, 2H), 3.76 (s, 4H), 7.20-
7.35 (m, 10H); 19F NMR (84.21 MHz) δ -118.57 (t, J ) 15.6
Hz, 2F), -84.61 (s, 3F); MS (EI) m/z (rel intensity) 329 (M+,
5), 210 (100); HRMS (EI) calcd for C17H16F5N (M+) 329.1203,
found 329.1204.
Typ ica l P r oced u r e for th e P r ep a r a tion of Yn a m in es
2. To a solution of LDA (2.2 mmol) in THF (3.0 mL) was
gradually added a solution of 1A (0.262 g, 1.0 mmol) in THF
(1.0 mL) and DMPU (0.282 g, 2.2 mmol) at 0 °C under argon.
The mixture was stirred at room temperature for 2 h. After
being quenched with water, the resulting mixture was ex-
tracted with ether (20 mL × 3). The combined extracts were
dried over anhydrous Na2SO4, filtered, and concentrated under
reduced pressure to leave crude 2A, of which the yield was
determined by 19F NMR using R,R,R-trifluorotoluene as the
reference. The ynamine 2A thus obtained was subjected to the
following reactions without any purification.
Calcd for C18H24F3NO: C, 66.04; H, 7.39; N, 4.28. Found: C,
66.48; H, 7.45; N, 4.07.
N,N-Dim eth yl-(Z)-3-p h en yl-2-(tr iflu or om eth yl)-2-p r o-
p en a m id e (3Ba ): mp 71-72 °C; IR (KBr) 1628 cm-1; 1H NMR
(300 MHz) δ 3.05 (s, 3H), 3.12 (s, 3H), 6.98 (s, 1H), 7.36-7.45
(m, 5H); 13C NMR (125.75 MHz) δ 34.92, 38.59, 121.70 (q, J )
274.7 Hz), 126.81 (q, J ) 32.7 Hz), 128.40, 128.96, 129.56,
132.34, 138.83 (q, J ) 4.0 Hz), 165.55 (q, J ) 2.3 Hz); 19F NMR
(84.21 MHz) δ -57.74 (s, 3F); MS (EI) m/z (rel intensity) 243
(M+, 31), 199 (100); HRMS (EI) calcd for C12H12F3NO (M+)
243.0871, found 243.0871. Anal. Calcd for C12H12F3NO: C,
59.26; H, 4.97; N, 5.76. Found: C, 59.54; H, 5.03; N, 5.34.
N,N-P en ta m eth ylen e-(Z)-3-p h en yl-2-(tr iflu or om eth yl)-
2-p r op en a m id e (3Ca ): IR (film) 1639 cm-1 1H NMR (300
;
MHz) δ 1.57-1.66 (m, 6H), 3.53-3.63 (m, 4H), 6.94 (s, 1H),
7.31-7.44 (m, 5H); 13C NMR (125.75 MHz) δ 24.22, 25.23,
26.00, 42.80, 48.19, 121.67 (q, J ) 274.9 Hz), 126.70 (q, J )
32.6 Hz), 128.29, 128.89, 128.90, 129.40, 132.33, 137.98 (q, J
) 3.2 Hz), 163.83 (q, J ) 2.4 Hz); 19F NMR (84.21 MHz) δ
-57.74 (s, 3F); MS (EI) m/z (rel intensity) 283 (M+, 24), 199
(100); HRMS (EI) calcd for C15H16F3NO (M+) 283.1184, found
283.1176.
N,N-Diisop r op yl-(Z)-3-p h en yl-2-(t r iflu or om et h yl)-2-
p r op en a m id e (3Da ): IR (film) 1639 cm-1 1H NMR (200
;
MHz) δ 1.24 (d, J ) 6.4 Hz, 6H), 1.50 (d, J ) 6.2 Hz, 6H),
3.41-3.60 (m, 1H), 4.11-4.30 (m, 1H), 6.86 (s, 1H), 7.35-7.46
(m, 5H); 13C NMR (125.75 MHz) δ 20.03, 20.15, 45.89, 51.14,
121.87 (q, J ) 274.8 Hz), 128.27, 128.61 (q, J ) 31.8 Hz),
128.87 (q, J ) 1.9 Hz), 129.23, 132.50, 136.15 (q, J ) 3.4 Hz),
164.40 (q, J ) 2.2 Hz); 19F NMR (84.21 MHz) δ -57.67 (s, 3F);
MS (EI) m/z (rel intensity) 299 (M+, 11), 199 (100); HRMS (EI)
calcd for C16H20F3NO (M+) 299.1498, found 299.1500.
N,N-Dibu tyl(3,3,3-tr iflu or o-1-p r op yn yl)a m in e (2A): bp
36 °C/15 Torr; IR (film) 2361 cm-1; 1H NMR (500 MHz) δ 0.94
(t, J ) 7.2 Hz, 6H), 1.31-1.43 (m, 4H), 1.55-1.65 (m, 4H),
2.98 (t, J ) 7.2 Hz, 4H); 13C NMR (125.75 MHz) δ 13.48, 19.71,
29.70, 52.56, 55.76 (q, J ) 52.08 Hz), 100.51 (q, J ) 7.12 Hz),
118.32 (q, J ) 255.01 Hz);19F NMR (84.21 MHz) δ -46.15 (s,
3F); MS (EI) m/z (rel intensity) 221 (M+, 19), 128 (100); HRMS
(EI) calcd for C11H18F3N (M+) 221.1391, found 221.1378.
N,N-Dim et h yl(3,3,3-t r iflu or o-1-p r op yn yl)a m in e (2B):
N,N-Dibu tyl-(Z)-3-(4-m eth ylph en yl)-2-(tr iflu or om eth yl)-
2-p r op en a m id e (3Ab): IR (film) 1630 cm-1 1H NMR (200
;
MHz) δ 0.92 (t, J ) 6.7 Hz, 3H), 0.96 (t, J ) 6.9 Hz, 3H), 1.22-
1.45 (m, 4H), 1.53-1.67 (m, 4H), 2.37 (s, 3H), 3.38 (t, J ) 7.6
Hz, 2H), 3.43 (t, J ) 7.6 Hz, 2H), 6.88 (s, 1H), 7.20 and 7.34
(AB quartet, J ) 8.2 Hz, 4H); 13C NMR (125.75 MHz) δ 13.57,
13.70, 19.79, 20.03, 21.18, 29.14, 30.40, 44.37, 48.43, 121.87
(q, J ) 274.5 Hz), 126.30 (q, J ) 32.3 Hz), 129.03, 129.05,
129.13, 129.52, 137.92 (q, J ) 4.0 Hz), 165.50 (q, J ) 2.1 Hz);
19F NMR (84.21 MHz) δ -55.02 (s, 3F); MS (EI) m/z (rel
intensity) 341 (M+, 5), 213 (100); HRMS (EI) calcd for C19H26F3-
NO (M+) 341.1966, found 341.1964. Anal. Calcd for C19H26F3-
NO: C, 66.84; H, 7.68; N, 4.10. Found: C, 66.57; H, 7.57; N,
3.79.
IR (THF soln) 2218 cm-1 19F NMR (84.21 MHz, THF) δ -46.21
;
(s, 3F). Other spectral data could not be obtained because of
contamination with the solvent.
N-(3,3,3-Tr iflu or o-1-p r op yn yl)p ip er id in e (2C): IR (film)
1
2222 cm-1; H NMR (500 MHz) δ 1.48-1.60 (m, 6H), 3.10 (t,
J ) 5.5 Hz, 4H); 13C NMR (125.75 MHz) δ 23.02, 24.62, 51.52,
52.96 (q, J ) 52.4 Hz), 98.83 (q, J ) 6.8 Hz), 117.77 (q, J )
254.4 Hz); 19F NMR (84.21 MHz) δ -46.34 (s, 3F).
N,N-Diisopr opyl(3,3,3-tr iflu or o-1-pr opyn yl)am in e (2D):
IR (film) 2203 cm-1; 1H NMR (500 MHz) δ 1.22 (d, J ) 6.5 Hz
12H), 3.19 (sept, J ) 6.5 Hz, 4H); 13C NMR (125.75 MHz) δ
21.23, 52.34, 60.73 (q, J ) 51.7 Hz), 98.71 (q, J ) 5.5 Hz),
118.65 (q, J ) 255.1 Hz);19F NMR (84.21 MHz) δ -44.77 (s,
3F).
N ,N -Dib u t yl-(Z)-3-(4-m e t h oxyp h e n yl)-2-(t r iflu or o-
m eth yl)-2-p r op en a m id e (3Ac): IR (film) 1640 cm-1 1H
;
NMR (200 MHz) δ 0.92 (t, J ) 7.2 Hz, 3H), 0.96 (t, J ) 7.3
Hz, 3H), 1.21-1.45 (m, 4H), 1.51-1.73 (m, 4H), 3.38 (t, J )
7.8 Hz, 2H), 3.43 (t, J ) 7.6 Hz, 2H), 3.84 (s, 3H), 6.82 (s, 1H),
6.91 and 7.41 (AB quartet, J ) 8.9 Hz, 4H); 13C NMR (125.75
MHz) δ 13.59, 13.71, 19.79, 20.05, 29.15, 30.40, 44.36, 48.43,
55.16,122.04 (q, J ) 274.3 Hz), 124.69, 124.75 (q, J ) 39.6
Hz), 131.05, 137.62 (q, J ) 3.9 Hz), 160.66, 165.73 (q, J ) 2.2
Hz); 19F NMR (84.21 MHz) δ -55.03 (s, 3F); MS (EI) m/z (rel
intensity) 357 (M+, 16), 229 (100); HRMS (EI) calcd for
Gen er a l P r oced u r e for th e Rea ction of 2 w ith Va r iou s
Ca r bon yl Com p ou n d s Lea d in g to R,â-Un sa tu r a ted
Am id es 3. To a solution of 2 (1.0 mmol) in CH2Cl2 (3.0 mL)
containing MS 4Å (1.0 g) were dropwise added successively
aldehyde (1.1 mmol) and BF3‚OEt2 (0.1 mmol) at 0 °C under
an argon atmosphere. After stirring at room temperature for
1 h, the mixture was filtered to remove MS 4Å. The filtrate
was poured into 3% HCl (10 mL), and the resulting mixture
was extracted with CH2Cl2 (10 mL × 3). The combined organic
layers were washed with brine (20 mL), dried over anhydrous
Na2SO4, and concentrated under reduced pressure to leave a
residual oil, which was submitted to 19F NMR analysis. The
residue was chromatographed on a silica gel column with
benzene to provide analytically pure product 3, together with
a small amount of 4 in some cases.
N,N-Dib u t yl-(Z)-3-p h en yl-2-(t r iflu or om et h yl)-2-p r o-
p en a m id e (3Aa ): IR (film) 1640 cm-1; 1H NMR (200 MHz) δ
0.94 (t, J ) 7.1 Hz, 3H), 0.96 (t, J ) 7.1 Hz, 3H), 1.23-1.46
(m, 4H), 1.53-1.68 (m, 4H), 3.39 (t, J ) 7.9 Hz, 2H), 3.44 (t,
J ) 7.6 Hz, 2H), 6.94 (s, 1H), 7.35-7.44 (m, 5H); 13C NMR
(125.75 MHz) δ 13.68, 13.79, 19.89, 20.10, 29.19, 30.48, 44.44,
48.49, 121.77 (q, J ) 274.7 Hz), 127.49 (q, J ) 32.6 Hz), 128.43,
128.90 (q, J ) 2.0 Hz), 129.44, 132.53, 137.9 (q, J ) 4.1 Hz),
165.5 (q, J ) 2.1 Hz); 19F NMR (84.21 MHz) δ -54.70 (s, 3F);
MS (EI) m/z (rel intensity) 327 (M+, 7), 199 (100); HRMS (EI)
calcd for C18H24F3NO (M+) 327.1810, found 327.1807. Anal.
C
C
19H26F3NO2 (M+) 357.1917, found 357.1910. Anal. Calcd for
19H26F3NO2: C, 63.85; H, 7.33; N, 3.92. Found: C, 64.04; H,
7.13; N, 3.84.
N,N-Dibu tyl-(Z)-3-(4-ch lor oph en yl)-2-(tr iflu or om eth yl)-
2-p r op en a m id e (3Ad ): IR (film) 1640 cm-1 1H NMR (200
;
MHz) δ 0.96 (t, J ) 7.0 Hz, 3H), 0.99 (t, J ) 7.0 Hz, 3H), 1.29-
1.44 (m, 4H), 1.55-1.70 (m, 4H), 3.40 (t, J ) 7.1 Hz, 2H), 3.47
(t, J ) 7.4 Hz, 2H), 6.90 (s, 1H), 7.39 (s, 4H); 13C NMR (125.75
MHz) δ 13.52, 13.64, 19.75, 19.97, 29.07, 30.35, 44.35, 48.46,
121.58 (q, J ) 275.0 Hz), 128.03 (q, J ) 32.2 Hz), 128.63,
130.15 (q, J ) 2.0 Hz), 130.85, 136.39 (q, J ) 3.7 Hz), 164.85
(q, J ) 2.1 Hz); 19F NMR (84.21 MHz) δ -55.03 (s, 3F); MS
(EI) m/z (rel intensity) 361 (M+, 6), 233 (100); HRMS (EI) calcd
for C18H23ClF3NO (M+) 361.1420, found 361.1413. Anal. Calcd
for C18H23ClF3NO: C, 59.75; H, 6.41; N, 3.87. Found: C, 60.00;
H, 6.51; N, 3.76.
N,N-Dibu tyl-(Z)-3-(1-n a p h th yl)-2-(tr iflu or om eth yl)-2-
p r op en a m id e (3Ae): mp 58.0-59.0 °C; IR (KBr) 1640 cm-1
;

3,3,3-Trifluoro-1-propynylamines
J . Org. Chem., Vol. 66, No. 10, 2001 3447
1H NMR (200 MHz) δ 0.98 (t, J ) 7.1 Hz, 3H), 1.00 (t, J ) 7.1
Hz, 3H), 1.30-1.50 (m, 4H), 1.58-1.79 (m, 4H), 3.50 (t, J )
7.4 Hz, 2H), 3.54 (t, J ) 6.5 Hz, 2H), 7.34 (s, 1H), 7.43-7.92
(m, 7H); 13C NMR (125.75 MHz) δ 13.74, 13.77, 20.04, 20.10,
29.23, 30.79, 44.52, 48.78, 121.75 (q, J ) 275.5 Hz), 124.02,
125.17, 126.21, 126.29 (q, J ) 2.5 Hz), 126.57, 128.66, 129.43,
130.24, 130.50 (q, J ) 31.4 Hz), 130.87, 133.12, 136.46 (q, J )
4.0 Hz), 164.96 (q, J ) 2.0 Hz); 19F NMR (84.21 MHz) δ -55.07
(s, 3F); MS (EI) m/z (rel intensity) 377 (M+, 9), 229 (100);
137.49 (q, J ) 3.3 Hz), 141.02, 165.21; 19F NMR (84.21 MHz)
δ -57.72 (s, 3F); MS (EI) m/z (rel intensity) 291 (M+, 4), 163
(100); HRMS (EI) calcd for C15H24F3NO (M+) 291.1811, found
291.1800.
N,N-Dibu tyl-(Z)-4-m eth yl-2-(tr iflu or om eth yl)-2,4-p en -
ta d ien a m id e (3Ak ): IR (film) 1643, 1646 cm-1; 1H NMR (300
MHz) δ 0.90 (t, J ) 7.2 Hz, 3H), 0.92 (t, J ) 7.2 Hz, 3H),
1.179-1.346 (m, 4H), 1.462-1.630 (m, 4H), 1.910 (s, 3H), 3.27
(t, J ) 7.8 Hz, 2H), 3.36 (t, J ) 7.5 Hz, 2H), 5.14 (s, 1H), 5.19
(s, 1H), 6.35 (s, 1H); 19F NMR (84.21 MHz) δ -55.94 (s, 3F);
MS (EI) m/z (rel intensity) 291 (M+, 14), 163 (100); HRMS (EI)
calcd for C15H24F3NO (M+) 291.1809, found 291.1815.
N ,N -Dib u t yl-(Z)-2-(t r iflu or om e t h yl)-2-h e xe n a m id e
HRMS (EI) calcd for
377.1961. Anal. Calcd for C22H26F3NO: C, 70.01; H, 6.94; N,
3.71. Found: C, 70.26 H, 7.03, N, 3.33.
C
22H26F3NO (M+) 377.1966, found
N,N-Dibu tyl-(Z)-3-(2-th ien yl)-2-(tr iflu or om eth yl)-2-pr o-
1
1
p en a m id e (3Af): mp 38.0-38.5 °C; IR (KBr) 1610 cm-1; H
(3Al): IR (film) 1640 cm-1; H NMR (200 MHz) δ 0.90-1.00
NMR (200 MHz) δ 0.90 (t, J ) 7.2 Hz, 3H), 0.95 (t, J ) 7.1
Hz, 3H), 1.23-1.60 (m, 8H), 3.35 (t, J ) 8.1 Hz, 2H), 3.42 (t,
J ) 7.2 Hz, 2H), 6.90 (s, 1H), 7.07 (dd, J ) 3.7, 5.0 Hz, 1H),
7.36 (d, J ) 3.7 Hz, 1H), 7.51 (d, J ) 5.0 Hz, 1H); 13C NMR
(125.75 MHz) δ 13.60, 13.76, 19.76, 20.09, 29.18, 30.42, 44.43,
48.45, 121.94 (q, J ) 273.9 Hz), 123.22 (q, J ) 33.4 Hz), 127.85,
129.74 (q, J ) 4.1 Hz), 130.52, 132.46 (q, J ) 2.4 Hz), 134.42,
165.24 (q, J ) 2.4 Hz); 19F NMR (84.21 MHz) δ -57.01 (s, 3F);
MS (EI) m/z (rel intensity) 333 (M+, 46), 264 (100); HRMS (EI)
calcd for C16H22F3NOS (M+) 333.1374, found 333.1372. Anal.
Calcd for C16H22F3NOS: C, 57.64; H, 6.65; N, 4.20. Found: C,
57.97; H, 6.59; N, 4.12.
(m, 9H), 1.22-1.60 (m, 10H), 2.33 (dtq, J ) 7.9, 7.5, 2.1 Hz,
2H), 3.26 (t, J ) 7.7 Hz, 2H), 3.37 (t, J ) 7.4 Hz, 2H), 6.00 (tq,
J ) 7.9, 0.8 Hz, 1H); 13C NMR (125.75 MHz) δ 13.58, 13.73,
19.79, 20.04, 21.81, 29.19, 30.28, 30.46, 44.33, 48.40, 122.10
(q, J ) 275.1 Hz), 128.78 (q, J ) 31.2 Hz), 141.43 (q, J ) 3.5
Hz), 165.24 (q, J ) 2.1 Hz); 19F NMR (84.21 MHz) δ -55.67
(br s, 3F); MS (EI) m/z (rel intensity) 293 (M+, 4), 165 (100);
HRMS (EI) calcd for
293.1964.
C
15H26F3NO (M+) 293.1968, found
N ,N -Dib u t yl-(Z)-2-(t r iflu or om e t h yl)-2-n on e n a m id e
(3Am ): IR (film) 1641 cm-1; 1H NMR (300 MHz) δ 0.87-0.96
(m, 9H), 1.24-1.58 (m, 16H), 2.34 (dtq, J ) 7.8, 7.5, 2.1 Hz,
2H), 3.26 (t, J ) 7.5 Hz, 2H), 3.37 (t, J ) 7.5 Hz, 2H), 6.00 (t,
J ) 7.8 Hz, 1H); 19F NMR (84.21 MHz) δ -58.32 (s, 3F); MS
(EI) m/z (rel intensity) 335 (M+, 19), 250 (100); HRMS (EI)
calcd for C20H26F3NO (M+) 335.2436, found 335.2438. Anal.
Calcd for C18H32F3NO: C, 64.45; H, 9.62; N, 4.18. Found: C,
64.42; H, 9.49; N, 4.01.
N,N-Dibu t yl-(Z)-3-(2-fu r yl)-2-(t r iflu or om et h yl)-2-p r o-
p en a m id e (3Ag): IR (film) 1643 cm-1; 1H NMR (300 MHz) δ
0.90 (t, J ) 7.5 Hz, 3H), 0.95 (t, J ) 7.5 Hz, 3H), 1.22-1.63
(m, 8H), 3.33 (t, J ) 7.5 Hz, 2H), 3.41 (t, J ) 7.5 Hz, 2H), 6.50
(dd, J ) 1.5, 3.6 Hz, 1H), 6.62 (s, 1H), 6.81 (d, J ) 3.6 Hz,
1H), 7.55 (d, J ) 1.5 Hz, 1H); 13C NMR (125.75 MHz) δ 13.58,
13.75, 19.74, 20.07, 29.16, 30.38, 44.38, 48.43, 112.40, 116.44
(q, J ) 2.2 Hz), 121.85 (q, J ) 273.7 Hz), 122.26 (q, J ) 34.4
Hz), 124.25 (q, J ) 3.5 Hz), 145.33, 147.41, 165.19 (q, J ) 2.3
Hz); 19F NMR (84.21 MHz) δ -60.22 (s, 3F); MS (EI) m/z (rel
intensity) 317 (M+, 23), 189 (100); HRMS (EI) calcd for
N,N-Dib u t yl-(Z)-4-m et h yl-2-(t r iflu or om et h yl)-2-p en -
ten a m id e (3An ): IR (film) 1650 cm-1; 1H NMR (200 MHz) δ
0.92 (t, J ) 7.1 Hz, 3H), 0.94 (t, J ) 7.2 Hz, 3H), 1.07 (d, J )
6.4 Hz, 6H), 1.20-1.63 (m, 8H), 2.79-2.99 (m, 1H), 3.26 (t, J
) 7.8 Hz, 2H), 3.37 (t, J ) 7.4 Hz, 2H), 5.78 (d, J ) 11.0 Hz,
1H); 13C NMR (125.75 MHz) δ 13.31, 13.44, 19.62, 19.81, 21.62,
28.00, 29.03, 30.25, 44.21, 48.27, 122.02 (q, J ) 275.0 Hz),
126.00 (q, J ) 31.5 Hz), 147.19 (q, J ) 3.4 Hz), 164.88 (q, J )
2.1 Hz); 19F NMR (84.21 MHz) δ -55.67 (br s, 3F); MS (EI)
m/z (rel intensity) 293 (M+, 5), 165 (100); HRMS (EI) calcd for
C
C
20H26F3NO (M+) 317.1602, found 317.1610. Anal. Calcd for
16H22F3NO2: C, 60.56; H, 6.99; N, 4.41. Found: C, 60.53; H,
6.94; N, 3.95.
N,N-Dibu tyl-(2Z,4E)-5-p h en yl-2-(tr iflu or om eth yl)-2,4-
p en ta d ien a m id e (3Ah ): mp 52.5-53.0 °C; IR (KBr) 1640
cm-1; 1H NMR (500 MHz) δ 0.91 (t, J ) 7.0 Hz, 3H), 0.95 (t, J
) 7.5 Hz, 3H), 1.20-1.58 (m, 8H), 3.32 (t, J ) 7.8 Hz, 2H),
3.41 (t, J ) 7.2 Hz, 2H), 6.58 (d, J ) 11.5 Hz, 1H), 6.83 (d, J
) 15.4 Hz, 1H), 7.13 (ddq, J ) 11.5, 15.4, 2.0 Hz, 1H), 7.27-
7.50 (m, 5H);13C NMR (125.75 MHz) δ 13.66, 13.81, 19.77,
20.11, 29.23, 30.47, 44.44, 48.52, 121.45, 122.32 (q, J ) 274.7
Hz), 125.40 (q, J ) 31.9 Hz), 127.36, 128.75, 129.37, 135.45,
137.24 (q, J ) 3.5 Hz), 141.87, 165.11 (q, J ) 2.3 Hz); 19F NMR
(84.21 MHz) δ -54.83 (br s, 3F); MS (EI) m/z (rel intensity)
353 (M+, 18), 225 (100); HRMS (EI) calcd for C20H26F3NO (M+)
353.1966, found 353.1966. Anal. Calcd for C20H26F3NO: C,
67.97; H, 7.42; N, 3.96. Found: C, 68.27; H, 7.46; N, 3.72.
N ,N -Dib u t yl-(2Z,4E )-4-flu or o-5-p h e n yl-2-(t r iflu or o-
m eth yl)-2,4-p en ta d ien a m id e (3Ai): IR (film) 1640 cm-1; 1H
NMR (500 MHz) δ 0.92 (t, J ) 7.5 Hz, 3H), 0.95 (t, J ) 7.5
Hz, 3H), 1.26-1.38 (m, 4H), 1.53-1.61 (m, 4H), 3.29-3.50 (m,
4H), 6.05 (d, J ) 34.1, Hz, 1H), 6.24 (d, J ) 30.0 Hz, 1H), 7.31-
7.61 (m, 5H); 13C NMR (125.75 MHz) δ 13.60, 13.76, 19.75,
20.07, 29.12, 30.32, 44.40, 48.31, 119.68 (q, J ) 9.1 Hz), 121.27
(q, J ) 273.1 Hz), 126.87 (dq, J ) 35.6, 4.40 Hz), 128.71,
128.90, 129.20, 129.68 (d, J ) 8.1 Hz), 132.12 (d, J ) 3.7 Hz),
152.67 (d, J ) 265.0 Hz), 164.65 (q, J ) 2.3 Hz); 19F NMR
(84.21 MHz) δ -56.91 (d, J ) 30.9 Hz, 3F), -113.30 (ddq, J )
30.0, 30.9, 34.1 Hz, 1F); MS (EI) m/z (rel intensity) 371 (M+,
24), 86 (100); HRMS (EI) calcd for C20H25 F4ON (M+) 371.1872,
found 371.1864.
C
15H26F3NO (M+) 293.1968, found 293.1970.
N,N-Dibu tyl-(Z)-3-cycloh exyl-2-(tr iflu or om eth yl)p r o-
p en a m id e (3Ao): IR (film) 1640 cm-1; 1H NMR (200 MHz) δ
0.92 (t, J ) 7.1 Hz, 3H), 0.93 (t, J ) 7.1 Hz, 3H), 1.02-1.77
(m, 18H), 2.45-2.69 (m, 1H), 3.25 (t, J ) 7.1 Hz, 2H), 3.37 (t,
J ) 7.5 Hz, 2H), 5.80 (dq, J ) 10.8, 0.8 Hz, 1H); 13C NMR
(125.75 MHz) δ 13.42, 13.51, 19.68, 19.87, 24.90, 25.36, 29.08,
29.36, 31.75, 37.66, 44.25, 48.34, 122.09 (q, J ) 275.2 Hz),
126.24 (q, J ) 31.4 Hz), 145.83, 165.07; 19F NMR (84.21 MHz)
δ -55.67 (br s, 3F); MS (EI) m/z (rel intensity) 333 (M+, 18),
250 (100); HRMS (EI) calcd for C18H30F3NO (M+) 333.2279,
found 333.2273.
N,N-Dibu tyl-(E)-4,4-dim eth yl-2-(tr iflu or om eth yl)-2-pen -
ten a m id e ((E)-3Ap ): IR (film) 1640 cm-1; 1H NMR (200 MHz)
δ 0.94 (t, J ) 7.2 Hz, 6H), 1.12 (s, 9H), 1.21-1.67 (m, 8H),
3.05-3.52 (m, 4H), 6.14 (q, J ) 1.5 Hz, 1H); 19F NMR (84.21
MHz) δ -61.42 (br s, 3F); MS (EI) m/z (rel intensity) 307 (M+,
3), 250 (100); HRMS (EI) calcd for C16H28F3NO (M+) 307.2123,
found 307.2118.
N,N-Dibu tyl-(Z)-4,4-dim eth yl-2-(tr iflu or om eth yl)-2-pen -
ten a m id e ((Z)-3Ap ): IR (film) 1645 cm-1; 1H NMR (200 MHz)
δ 0.93 (t, J ) 7.2 Hz, 3H), 0.94 (t, J ) 7.7 Hz, 3H), 1.21 (s,
9H), 1.27-1.76 (m, 8H), 3.21-3.36 (m, 4H), 5.93 (s, 1H); 13C
NMR (125.75 MHz) δ 13.68, 13.74, 20.16, 20.35, 28.48, 28.72,
29.81, 34.12, 44.10, 49.09, 122.64 (q, J ) 274.5 Hz), 124.44 (q,
J ) 29.9 Hz), 146.08 (q, J ) 15.1 Hz), 163.57; 19F NMR (84.21
MHz) δ -53.25 (s, 3F); MS (EI) m/z (rel intensity) 307 (M+,
3), 250 (100); HRMS (EI) calcd for C16H28F3NO (M+) 307.2123,
found 307.2125. Anal. Calcd for C16H28F3NO: C, 62.52; H, 9.18;
N, 4.56. Found: C, 62.60; H, 9.20; N, 4.43.
N,N-Dibu tyl-(2Z,4E)-2-(tr iflu or om eth yl)-2,4-h exa d ien -
a m id e (3Aj): IR (film) 1640 cm-1; 1H NMR (200 MHz) δ 0.92-
0.96 (m, 6H), 1.26-1.56 (m, 8H), 1.89 (d, J ) 6.8 Hz, 3H), 3.28
(t, J ) 7.6 Hz, 2H), 3.38 (t, J ) 7.4 Hz, 2H), 6.10 (dq, J ) 13.6,
6.8 Hz, 1H), 6.34-6.48 (m, 2H); 13C NMR (125.75 MHz) δ
13.44, 13.59, 18.48, 19.59, 19.94, 29.10, 30.33, 44.17, 48.29,
122.17 (q, J ) 274.6 Hz), 123.34 (q, J ) 31.8 Hz), 125.20,
N ,N -Dib u t yl-3-m e t h yl-2-(t r iflu or om e t h yl)-2-b u t e n -
a m id e (3Aq): IR (film) 1640 cm-1; 1H NMR (200 MHz) δ 0.92
(t, J ) 7.2 Hz, 3H), 0.94 (t, J ) 7.2 Hz, 3H), 1.19-1.65 (m,

3448 J . Org. Chem., Vol. 66, No. 10, 2001
Mantani et al.
8H), 1.81 (q, J ) 2.2 Hz, 3H), 1.96 (q, J ) 2.0 Hz, 3H), 3.22
(dd, J ) 6.8, 9.1 Hz, 2H), 3.35 (dt, J ) 13.5, 7.6 Hz, 1H), 3.45
(dt, J ) 13.5, 7.7 Hz, 1H); 19F NMR (84.21 MHz) δ -54.53 (br
s, 3F); MS (EI) m/z (rel intensity) 279 (M+, 4), 151 (100); HRMS
(EI) calcd for C14H24F3NO (M+) 279.1811, found 279.1809.
Anal. Calcd for C14H24F3NO: C, 60.20; H, 8.66; N, 5.01.
Found: C, 60.16; H, 8.68; N, 4.82.
N ,N -Dib u t yl-3-e t h yl-2-(t r iflu or om e t h yl)-2-p e n t e n -
a m id e (3Ar ): IR (film) 1635 cm-1; 1H NMR (200 MHz) δ 0.91
(t, J ) 6.6 Hz, 3H), 0.95 (t, J ) 6.4 Hz, 3H), 1.07 (t, J ) 7.5
Hz, 3H), 1.09 (t, J ) 7.5 Hz, 3H), 1.18-1.64 (m, 8H), 2.00-
2.50 (m, 4H), 3.18-3.51 (m, 4H); 13C NMR (125.75 MHz) δ
11.69, 12.14, 19.70, 19.92, 23.23, 25.80, 28.76, 29.96, 43.80,
47.98, 122.30 (q, J ) 274.9 Hz), 123.46 (q, J ) 30.7 Hz), 154.64
(q, J ) 3.6 Hz), 164.48 (q, J ) 2.1 Hz); 19F NMR (84.21 MHz)
δ -54.11 (br s, 3F); MS (EI) m/z (rel intensity) 307 (M+, 7),
179 (100); HRMS (EI) calcd for C16H28F3NO (M+) 307.2124,
found 307.2123.
HRMS (EI) calcd for C11H20F3NO (M+) 239.1498, found
239.1493. Anal. Calcd for C11H20F3NO: C, 55.22; H, 8.42; N,
5.85. Found: C, 55.12; H, 8.28; N, 5.79.
N,N-Dim et h yl-3,3,3-t r iflu or op r op a n a m id e (4B): mp
43.8-44.7 °C; IR (KBr) 1665 cm-1; 1H NMR (200 MHz) δ 3.01
(s, 3H), 3.08 (s, 3H), 3.26 (q, J ) 10.1 Hz, 2H); 13C NMR (125.75
MHz) δ 35.47, 37.64, 37.98 (q, J ) 28.5 Hz), 124.13 (q, J )
276.6 Hz), 163.08 (q, J ) 2.9 Hz); 19F NMR (84.21 MHz) δ
-60.66 (t, J ) 10.1 Hz, 3F); MS (EI) m/z (rel intensity) 155
(M+, 100); HRMS (EI) calcd for C5H8F3NO (M+) 155.0558,
found 155.0558. Anal. Calcd for C5H8F3NO: C, 38.71; H, 5.20;
N, 9.03. Found: C, 38.67; H, 5.15; N, 9.03.
N-(3,3,3-Tr iflu or op r op a n oyl)p ip er id in e (4C): IR (film)
1
1640 cm-1; H NMR (200 MHz) δ 1.52-1.73 (m, 6H), 3.24 (q,
J ) 10.2 Hz, 2H), 3.39-3.62 (m, 4H); 13C NMR (125.75 MHz)
δ 24.18, 25.28, 26.25, 38.00 (q, J ) 28.9 Hz), 42.94, 47.43,
124.22 (q, J ) 276.8 Hz), 161.25 (q, J ) 3.0 Hz); 19F NMR
(84.21 MHz) δ -60.53 (t, J ) 10.2 Hz, 3F); MS (EI) m/z (rel
intensity) 195 (M+, 100); HRMS (EI) calcd for C8H12F3NO (M+)
195.0872, found 195.0860. Anal. Calcd for C8H12F3NO: C,
49.23; H, 6.20; N, 7.18. Found: C, 49.58; H, 5.84; N, 7.05.
N,N-Diisop r op yl-3,3,3-tr iflu or op r op a n a m id e (4D): IR
N,N-Dibu tyl-2-(cycloh exyliden e)-3,3,3-tr iflu or opr opan -
a m id e (3As): IR (film) 1640 cm-1; 1H NMR (200 MHz) δ 0.92
(t, J ) 7.1 Hz, 3H), 0.94 (t, J ) 7.2 Hz, 3H), 1.19-1.75 (m,
14H), 1.92-2.52 (m, 4H), 3.13-3.43 (m, 4H); 13C NMR (125.75
MHz) δ 13.36, 13.49, 19.71, 19.99, 25.53, 27.26, 28.88, 30.16,
30.70, 32.73, 43.87, 47.98, 121.27 (q, J ) 30.7 Hz), 122.30 (q,
J ) 274.9 Hz), 151.75 (q, J ) 3.6 Hz), 164.54 (q, J ) 1.7 Hz);
19F NMR (84.21 MHz) δ -53.28 (br s, 3F); MS (EI) m/z (rel
intensity) 319 (M+, 11), 191 (100); HRMS (EI) calcd for
1
(film) 1655 cm-1; H NMR (300 MHz) δ 1.40 (d, J ) 6.6 Hz,
6H), 2.47 (d, J ) 6.9 Hz, 6H), 3.21 (q, J ) 10.2 Hz, 2H), 3.53
(sept, J ) 6.9 Hz, 1H), 3.89 (sept, J ) 6.6 Hz, 1H); 13C NMR
(125.75 MHz) δ 20.20, 20.70, 39.58 (q, J ) 28.2 Hz), 46.24,
49.52, 124.30 (q, J ) 276.7 Hz), 161.68 (q, J ) 2.3 Hz); 19F
NMR (84.21 MHz) δ -62.85 (t, J ) 10.2 Hz, 3F); MS (EI) m/z
(rel intensity) 211 (M+, 24), 154 (100); HRMS (EI) calcd for
C9H16F3NO (M+) 211.1184, found 211.1189. Anal. Calcd for
C9H16F3NO: C, 51.18; H, 7.64; N, 6.63. Found: C, 50.91; H,
7.57; N, 6.54.
C
17H28F3NO (M+) 319.2124, found 319.2120.
N,N-Dibu tyl-(E)-3-p h en yl-2-(tr iflu or om eth yl)-2-bu ten -
a m id e ((E)-3At): IR (film) 1635 cm-1; 1H NMR (300 MHz) δ
0.74-1.42 (m, 14H), 2.29 (q, J ) 2.1 Hz, 3H), 2.59-2.91 (m,
2H), 3.11-3.52 (m, 2H), 7.33 (s, 5H); 13C NMR (125.75 MHz)
δ 13.36, 13.49, 19.71, 19.99, 25.53, 27.26, 28.88, 30.16, 30.70,
32.73, 43.87, 47.98, 121.27 (q, J ) 30.7 Hz), 122.30 (q, J )
274.9 Hz), 151.75 (q, J ) 3.6 Hz), 163.46; 19F NMR (84.21 MHz)
δ -57.72 (q, J ) 2.1 Hz, 3F); MS (EI) m/z (rel intensity) 341
(M+, 5), 213 (100); HRMS (EI) calcd for C19H26F3NO (M+)
341.1968, found 341.1973.
X-r a y Cr ysta l Str u ctu r e Deter m in a tion for 3Ba . A
colorless prismatic crystal of approximate dimensions 0.20 ×
0.20 × 0.20 mm3 was mounted on thin glass fiber with epoxy
cement. Data were collected on a Rigaku AFC7R diffractometer
with graphite monochromated Cu KR radiation and a rotating
anode generator. The material crystallizes in the monoclinic
space group C2/c with a ) 25.588 (2) Å, b ) 6.724 (2) Å, c )
14.397 (2) Å, â ) 107.332 (9)°, V ) 2364.5 (7) Å3, and Z ) 8.
Data collection, reduction, solution, and refinement were all
carried out using teXsan7 crystallographic software package
of Molecular Structure Corporation. All non-H atoms were
refined anisotropically; 1679 observations, 203 variables; R1
) 0.063 for F2 > 4σ(F2) and wR2 ) 0.074 for all F2.
N,N-Dibu tyl-(Z)-3-p h en yl-2-(tr iflu or om eth yl)-2-bu ten -
a m id e ((Z)-3At): IR (film) 1640 cm-1; 1H NMR (300 MHz) δ
0.97 (t, J ) 7.5 Hz, 3H), 0.98 (t, J ) 7.2 Hz, 3H), 1.26-1.69
(m, 8H), 2.09 (q, J ) 2.0 Hz, 3H), 3.35-3.59 (m, 4H), 7.19-
7.43 (m, 5H); 13C NMR (75.61 MHz) δ 13.75, 13.82, 20.22,
20.36, 24.52, 29.28, 30.53, 44.43, 48.41, 121.90 (q, J ) 274.7
Hz), 125.72 (q, J ) 30.8 Hz), 126.59, 128.11, 128.25, 139.50,
147.26 (q, J ) 3.8 Hz), 164.60; 19F NMR (84.21 MHz) δ -55.23
(q, J ) 2.1 Hz,3F); MS (EI) m/z (rel intensity) 341 (M+, 4), 213
(100); HRMS (EI) calcd for C19H26F3NO (M+) 341.1968, found
341.1963.
N,N-Dibu tyl-3,3,3-tr iflu or op r op a n a m id e (4A): IR (film)
1660 cm-1; 1H NMR (200 MHz) δ 0.93 (t, J ) 7.3 Hz,3H), 0.96
(t, J ) 7.3 Hz, 3H), 1.22-1.64 (m, 8H), 3.20 (q, J ) 10.0 Hz,
2H), 3.24 (t, J ) 7.8 Hz, 2H), 3.35 (t, J ) 7.5 Hz, 2H); 13C
NMR (125.75 MHz) δ 13.50, 13.57, 19.81, 19.95, 29.42, 30.92,
37.61 (q, J ) 28.6 Hz), 45.75, 47.98, 124.15 (q, J ) 276.5 Hz),
162.46 (q, J ) 3.4 Hz); 19F NMR (84.21 MHz) δ -60.50 (t, J )
10.0 Hz, 3F); MS (EI) m/z (rel intensity) 239 (M+, 3), 86 (100);
Ack n ow led gm en t. We are grateful to Central Glass
Co., Ltd., J apan and Daikin Industry, Co., Ltd., J apan
for their generous gifts of trifluoromethanesulfonic
anhydride and pentafluoropropanol, respectively.
Su p p or tin g In for m a tion Ava ila ble: X-ray crystallo-
graphic data and an ORTEP diagram for compound 3Ba . This
material is available free of charge via the Internet at
http://pubs.acs.org.
J O001760V