Scope and limitation of intramolecular Pauson-Khand reaction of fluorine-containing enynes

Article abstract of DOI:10.1016/S0022-1139(01)00436-5

Intramolecular Pauson-Khand reaction of various fluorine-containing enynes was investigated under various conditions. The reaction of the substrates, which have fluorine atom(s) or fluorine-containing group(s) attached to alkenyl moiety, gave the corresponding cyclopentenones in low to moderate yield, while that of the substrates bearing fluorine-containing groups attached to alkynyl moiety afforded the corresponding cyclopentenones in low to high yield.

Full text of DOI:10.1016/S0022-1139(01)00436-5

Journal of Fluorine Chemistry 111 02001) 81±90
Scope and limitation of intramolecular Pauson±Khand
reaction of ¯uorine-containing enynes
Miyuki Ishizaki*, Daisuke Suzuki, Osamu Hoshino1
Faculty of Pharmaceutical Sciences, Science University of Tokyo, 12, Ichigaya Funagawara-machi,
Shinjuku-ku, Tokyo 162-0826, Japan
Received 23 March 2001; received in revised form 17 May 2001; accepted 25 June 2001
Abstract
Intramolecular Pauson±Khand reaction of various ¯uorine-containing enynes was investigated under various conditions. The reaction of
the substrates, which have ¯uorine atom0s) or ¯uorine-containing group0s) attached to alkenyl moiety, gave the corresponding
cyclopentenones in low to moderate yield, while that of the substrates bearing ¯uorine-containing groups attached to alkynyl moiety
afforded the corresponding cyclopentenones in low to high yield. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Pauson±Khand reaction; Fluorine-containing cyclopentenone; Fluroalkene; Fluoroalkyne
1. Introduction
2. Results and discussion
The introduction of ¯uorine atom0s) into organic mole-
cules strongly effected their chemical, biological, and phy-
sical properties by steric factor, high electoronegativity,
and lipophilicity [1±8]. Many new ¯uorinated materials
such as drugs [3,4] and agrochemicals [5] take advantage
of these effective changes. Additionally, applications in
material sciences such as dyes [6], polymers [7], and liquid
crystals [8] have attracted organic chemists' attention. Since
®rst report [9] of Pauson±Khand reaction in 1971, the reaction
has been used as powerful tool for construction of cyclopen-
tenone derivatives [10±14]. However, application of the reac-
tion to ¯uorine-containing substrates has appeared very little
[15] and no systematic studies have been done. Here, we wish
to describe systematic studies on intramolecular Pauson±
Khand reaction of various ¯uorine-containing enynes
0Scheme 1).
2.1. Synthesis of fluorine-containing substrates
Various enynes 01±16) bearing ¯uorine atom0s) or ¯uor-
ine-containing groups on alkenyl or alkynyl moiety were
prepared as depicted in Schemes 2 and 3, respectively. Thus,
di¯uoromethylenation [16] of aldehyde 034) [17] afforded
di¯uoroalkene 01) in 50% yield. Reduction [16] of 1 with
Vitride1 furnished mono¯uoroalkene 02) as 1:1 mixture
of regioisomers in 34% yield. Aldehyde 034) was also
converted to 3 as 71:29 mixture of regioisomers by chlor-
otri¯uoroethylenation [18]. Unfortunately, attempts for
reductive dechlorination of 3 with LiAlH4 in THF or NaBH4
in diglyme [19] failed. Enyne 04) containing a ¯uorophenyl
group was obtained by Wittig ole®nation of 4-¯uoroben-
zaldehyde with 35 [20]. Tri¯uoromethyl alcohols 05, 6) were
synthesized from 34 via Honor±Emmons type ole®nation,
reduction and tri¯uoromethylation [21] 0during tri¯uoro-
methylation of carbonyl compounds 037, 38), we found
convenient trimethylsilylation of terminal alkynes) see [22].
Formylation of 39 [23] followed by tri¯uoromethylation
[24] furnished tri¯uoromethyl alcohol 016), oxidation of
which with Dess±Martin periodinane produced tri¯uoro-
methyl ketone 010).2 Fluoro-containing arylalkynes 07±9,
* Corresponding authors. Tel.: ‡81-3-3260-4272/ext. 5038;
fax: ‡81-3-3268-3045.
E-mail addresses: ishizaki@ps.kagu.sut.ac.jp 0M. Ishizaki),
hoshino@ps.kagu.sut.ac.jp 0O. Hoshino).
1 Co-corresponding author. Tel.: ‡81-3-5228-8378;
fax: ‡81-3-3268-3045.
2 All attempts for direct synthesis of 10 from 39 with BuLi followed by
the treatment with ꢀCF3CO)2O or CF3CO2Et failed.
0022-1139/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 0 0 1 ) 0 0 4 3 6 - 5

82
M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
11±13) were obtained by palladium catalyzed coupling
[25] of 39 or 41 [26] with corresponding ¯uoroiodobenzenes.
Enynes 014, 15) containing ¯uoroaryl alcohols were synthe-
sized from 39 by the reaction of BuLi and appropriate
¯uoroaldehydes.
Scheme 1.
Scheme 2. 0a) Zn, CF2Br2, PPh3, MeCONMe2, 1008C, 2 h; 0b) Vitride1, benzene, D, 3 h; 0c) CF3CCl3, PPh3, CH3CN, rt, 1.5 h; 0d) 0EtO)2POCH2CO2Et,
NaH, THF, rt, 1 h; 0e) MeC0=O)CHPPh3, benzene, D, 1 h; 0f) DIBAH, toluene, À788C, 0.5 h, Dess±Martin periodinane, CH2Cl2, rt, 0.5 h; 0g) CF3TMS, CsF,
DME, rt, 0.5±3 h; 0h) 4-FC6H4CHO, t-BuOK, THF, rt, 3 h.
Scheme 3. 0a) BuLi, THF then DMF, À788C, 20 min; 0b) CF3TMS, TBAF, THF, 08C, 10 min; 0c) Dess±Martin periodinane, CH2Cl2, rt, 0.5 h; 0d) 4-
CF3C6H4I or 4-FC6H4I or C6F5I, PdCl20PPh3)2, CuI, Et3N, CH2Cl2, rt or 408C, 0.5±3 h; 0e) BuLi, THF then 4-CF3C6H4CHOor 4-FC 6H4CHO, À788C, 1 h.

M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
83
Table 1
methods; treatment with NMO0 N-methylmorpholine N-
oxide) [27] in CH2Cl2 at rt 0method A) or re¯uxing in
toluene 0method B).
Pauson±Khand reaction of various fluorine-containing enynes
Entry
Substrate
Methoda
Time 0h)
Product
Yield 0%)
At ®rst, we investigated the reaction of enynes 01±6),
which have ¯uorine group0s) attached to alkenyl moiety
0Table 1 and Fig. 1). In the reaction of di¯uoroole®n 01),
decomposition was observed in both methods A and B
to give no cyclized product. This ®ndings appeared to
imply poor reactivity of ole®n due to high electoronega-
tivity of ¯uorine atom 0for the successful report of Pauson±
Khand reaction of activated ole®ns, see [28±30]). With
mono¯uoroole®n 02), the reaction proceeded with de¯uor-
ization to afford de¯uorized cyclopentenone 019) [31]
instead of 18 0entry 1) 0similar dehalogenation was repor-
tedin the Pauson±Khand reaction of haloalkenes [32]).
Furthermore, the reaction of tri¯uoromethyl-substituted
ole®n 03) underwent dechlorination [32] to furnish 20 as
a single diastereomer in 14% yield 0entry 3), while that using
method B did not at all produce 20. Stereochemistry of
20 was con®rmed by NOE experiment. Similarly, 4-¯uor-
oarylole®n 04) produced stereoselectively trans-oriented
arylcyclopentenone 021) [33] in 23% yield by method A
0entry 5). The reaction of tri¯uoromethyl-substituted
allylic alcohols 05, 6) using method A afforded in moderate
yield 031±34%) corresponding cyclized products 022, 23)
as an inseparable diastereomeric mixture together with
starting materials 05, 6), however, in low yield 04±12%)
by method B 0entries 7±10). When enynes having ¯uorine
atom0s) or ¯uorine-containing groups attached to ole®n
moiety was employed, method A was found to be superior
to method B, although the yield of desired products was
unsatisfactory.
1
2
2
2
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
1
19
37
2
18 or 19
20
20
0
14
3b
3
1
4
3
3
0
5
4
1
21
21
23 018)c
6
4
3
2
7
5
1
22
22
31d 04)c
4d 012)c
34d 05)c
12d 020)c
42
8
5
5
9
6
1
23
23
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
6
3
7
0.5
7
24
24
7
55
8
0.5
7
25
25
14
52
8
9
0.5
1
26
26
15
9
33
11
11
12
12
13
13
14
14
15
15
16
0.5
1
28
28
92
62
0.5
1
29
29
85
67
87
0.5
1
30
30
49
0.5
2
31L ‡ 31He 42 ‡ 25
31
0
0.5
2
32L ‡ 32He 41 ‡ 25
32
33
0
85f
0.5
a See text.
b The reaction was performed at 08C.
c Value in parenthesis was recovery of starting material.
d Obtained as an inseparable mixture of diastereomers, although the
ratio was not determined.
e Stereochemistry of each product was not determined. L and H mean
low and high polar products on TLC.
f An inseparable 1:1 mixture of diastereomers.
Next, we investigated the reaction of enynes 07±16)
bearing ¯uorine groups on alkynyl moiety. In the reaction
of ¯uoroaromatic enynes 07±9), corresponding cyclized
products 024±26) were obtained in 14±55% yields 0entries
11±16). Contrary to the reaction of enynes 03±5) having
¯uorine-containing groups on alkene moiety, method
B was superior to method A in these reactions,
although the reason was uncertain. On the other hand,
2.2. Pauson±Khand reaction of fluorine-containing
substrates
With ¯uorine-containing enynes 01±16) in hand, intramo-
lecular Pauson±Khand reaction was performed by following
Fig. 1. Products in Pauson-Khand reaction of fluorine-containing enzymes.

84
M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
the reaction of ¯uoroaromatic enynes 011±13) derived
from dimethyl malonate produced corresponding cyclo-
pentenones 028±30) in high yield 085±92%) by method
A. Surprisingly, no desired products were obtained
from tri¯uoromethyl ketone 010) in both methods A
and B.2 For the successful reports of Pauson±Khand
reaction of electron de®cient alkynes 0see [34,35]). The
reaction of markedly electron de®cient alkyne recovered
cobalt±alkyne complex 0see [36]). Fluorine substituted
propargyl alcohols 014±16) furnished a mixture of diaster-
eomers of corresponding cyclopentenones 031±33) in
good yield 067±85%) by method A 0entries 23, 25, 27).
Thus, the reaction of enynes having ¯uorine atom0s)
attached to alkyne moiety was found to give correspond-
ing cyclized products in moderate to high yield except
for enyne 010) bearing marked electron withdrawing
groups.
4.2. N-.3,3-difluoro-2-propenyl)-N-.2-propynyl)tosylamide
.1)
To a solution of 34 01.845 g, 7.18 mmol), PPh3 03.930 g,
15 mmol), and CBr2F2 03.147 g, 15 mmol) in dimethylace-
tamide 015 ml) was added Zn dust 00.980 g, 15 mmol). After
the mixture was heated at 1008C for 2 h, the reaction was
quenched with water. The mixture was extracted with Et2O.
The organic extracts were washed with brine, dried, and
evaporated under reduced pressure to give an oily residue,
which was puri®ed by column chromatography 0AcOEt:
hexane ˆ 1:10) to afford 1 01.021 g, 50%) as crystals; mp
1
49±508C; H NMR d 7.73, 7.31 0each 2H, d, J ˆ 8:3 Hz),
4.21±4.37 01H, m), 4.10 02H, d, J ˆ 2:3 Hz), 3.89 02H, d,
J ˆ 7:9 Hz), 2.43 03H, s), 2.07 01H, t, J ˆ 2:3 Hz); IR 3261,
‡
2119, 1595 cmÀ1; MS m/z 285 0M ); high-resolution mass m/
‡
z calcd for C13H13F2NO2S 0M ) 285.0634, found: 285.0625.
4.3. N-.3-fluoro-2-propenyl)-N-.2-propynyl)tosylamide .2)
3. Conclusion
A mixture of 1 01.12 g, 3.94 mmol) and Vitride1 02.0 ml,
65% in toluene) in benzene 08 ml) was re¯uxed for 3 h.
Usual work-up gave an oily residue, which was puri®ed by
column chromatography 0AcOEt:hexane ˆ 1:8) to afford 2
We have investigated Pauson±Khand reaction of various
¯uorine-containing enynes. Feature of the present reaction
was as follows. 01) In the reaction of enynes, which have
¯uoro-functional groups on alkene moieties, desired
cyclopentenones were obtained in low to moderate yields.
02) In the reaction of enynes bearing ¯uoro-functional
groups on alkynyl moiety, the corresponding cyclized
products were formed in moderate to high yields. 03) In
each case, method A was found to superior to method B
except for 7±9.
1
00.360 g, 34%) as crystals; mp 50±518C; H NMR d 7.74,
7.31 0each 2H, d, J ˆ 8:6 Hz), 6.82, 6.51 0each 0.5H, d,
J ˆ 11:2 Hz), 5.24±5.40 01H, m), 4.10 02H, d, J ˆ 2:3 Hz),
3.77 02H, d, J ˆ 7:9 Hz), 2.43 03H, s), 2.05 01H, t,
J ˆ 2:3 Hz); IR 3259, 2118, 1596 cmÀ1; MS m/z 267
‡
‡
0M ); high-resolution mass m/z calcd for C13H14FNO2S
0M ) 267.0719, found: 267.0728.
The present study offers alternative approach to ¯uoro-
containing cyclopentenone derivatives.
4.4. N-.3-chloro-4,4,4-trifluoro-2-butenyl)-N-.2-
propynyl)tosylamide .3)
4. Experimental
To a mixture of 34 02.57 g, 10.0 mmol) and PPh3 014.1 g,
53.9 mmol) in CH3CN 060 ml) was added at 08C under
argon CF3CCl3 03.2 ml, 27 mmol) in one portion. After
being stirred for 1.5 h, the solvent was evaporated under
reduced pressure to give a residue, to which was added Et2O.
The precipitate was removed by suction and the ®ltrate was
evaporated under reduced pressure to give a residue, which
was puri®ed by column chromatography 0AcOEt:hexane ˆ
4.1. General
All melting points were measured on a BuÈchi or a
Yanagimoto 0hot plate) melting point apparatus and are
uncorrected. IR spectra were performed with a Hitachi
260-10 spectrophotometer in CHCl3 solution, and 1H
NMR spectra were taken with a JEOL EX-270 0270
MHz) spectrometer in CDCl3 solution with tetramethylsi-
lane as an internal standard. Mass spectra were measured on
a Hitachi M-80 or a JEOL JMS D-300 spectrometer. Column
chromatography was performed over silica gel 0Merck
Kiegelsel 60). Preparative TLCs were run on Merck 7730
plates. Organic extracts were dried over MgSO4, unless
otherwise indicated.
1
1:10) to afford 3 00.687 g, 20%) as a pale yellow oil; H
NMR d 7.72, 7.32 0each 2H, d, J ˆ 8:3 Hz), 6.51 00.71H, t,
J ˆ 6:3 Hz), 6.24 00.29H, t, J ˆ 6:6 Hz), 4.09 02H, d,
J ˆ 2:5 Hz), 4.05±4.13 02H, m), 2.43 03H, s), 2.12 01H, t,
J ˆ 2:5 Hz); IR 2926, 2118, 1655, 1598 cmÀ1; MS m/z 351
‡
‡
0M ); high-resolution mass m/z calcd for C14H13ClF3NO2S
0M ) 351.0308, found: 351.0317.
4.5. .2E)-N-[3-.4-fluorophenyl)-2-propenyl]-N-.2-
propynyl)tosylamide .4)
2 The reaction of 10 in refluxing CH3CN [34] also did not give desired
product ꢀ27).
To a mixture of 4-¯uorobenzaldehyde 00.296 g, 2.38
mmol) and Wittig reagent 035, 1.25 g, 2.0 mmol) in THF

M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
85
020 ml) was added at rt t-BuOK 00.288 g, 2.36 mmol) in one
4.8. .2E)-N-.4-oxo-2-pentenyl)-N-.2-propynyl)tosylamide
.38)
portion. After being stirred for 3 h, the reaction was
quenched with water. Work-up similar to that noted for 1
gave an oily residue, which was puri®ed by column chro-
matography 0AcOEt:hexane ˆ 1:5) to afford 4 00.189 g,
A mixture of 34 00.534 g, 2.1 mmol) and 1-0triphenylpho-
sphanylidene)-2-propanone 00.664 g, 2.1 mmol) in benzene
010 ml) was re¯uxed for 1 h. The solvent was evaporated
under reduced pressure to give an oily residue, which was
puri®ed by column chromatography 0AcOEt:hexane ˆ 1:2)
1
28%) as a colorless oil; H NMR d 7.70, 7.28 0each 2H,
d, J ˆ 8:3 Hz), 7.19 02H, dd, J ˆ 5:6, 8.6 Hz), 7.01 02H, t,
J ˆ 8:6 Hz), 6.63 01H, d, J ˆ 11:7 Hz), 5.63 01H, dt,
J ˆ 5:8, 11.7 Hz), 4.09 02H, d, J ˆ 2:3 Hz), 4.08 02H, d,
J ˆ 5:8 Hz), 2.42 03H, s), 1.86 01H, t, J ˆ 2:3 Hz); MS m/z
1
to afford 38 00.541 g, 90%) as a colorless oil; H NMR d
7.73, 7.31 0each 2H, d, J ˆ 8:3 Hz), 6.63 01H, dt, J ˆ 5:8,
15.8 Hz), 6.22 01H, d, J ˆ 15:8 Hz), 4.09 02H, d,
J ˆ 2:6 Hz), 3.99 02H, d, J ˆ 5:8 Hz), 2.43, 2.25 0each
3H, s), 2.07 01H, t, J ˆ 2:6 Hz); IR 2924, 2118, 1734,
‡
343 0M ); high-resolution mass m/z calcd for C19H18FNO2S
‡
0M ) 343.1042, found: 343.1040.
‡
4.6. .2E)-N-.3-ethoxycarbonyl-2-propenyl)-N-.2-
propynyl)tosylamide .36)
1680, 1598 cmÀ1; MS m/z 291 0M ); high-resolution mass
‡
m/z calcd for C15H17NO3S 0M ) 291.0929, found: 291.0933.
After a mixture of NaH 00.142 g, 3.55 mmol) and ethyl
diethylphosphonoacetate 00.807 g, 3.6 mmol) in THF
010 ml) was stirred at rt for 10 min, a solution of 34
00.767 g, 3 mmol) in THF 010 ml) was added. Then the
mixture was stirred for 1 h. The reaction was quenched
with 3 M HCl. Work-up similar to that noted for 1 gave an
oily residue, which was puri®ed by column chromatogra-
phy 0AcOEt:hexane ˆ 1:2) to afford 36 00.692 g, 72%) as
a colorless oil; 1H NMR d 7.73, 7.30 0each 2H, d,
J ˆ 8:3 Hz), 6.79 01H, dt, J ˆ 5:8, 15.5 Hz), 6.02 01H,
d, J ˆ 15:5 Hz), 4.19 02H, q, J ˆ 7:1 Hz), 4.09 02H, d,
J ˆ 2:6 Hz), 3.97 02H, d, J ˆ 5:8 Hz), 2.42 03H, s), 2.05
01H, t, J ˆ 2:6 Hz), 1.28 03H, t, J ˆ 7:1 Hz); IR
4.9. .2E)-N-.5,5,5-trifluoro-4-hydroxy-2-pentenyl)-N-.2-
propynyl)tosylamide .5)
To a solution of 37 00.277 g, 1.0 mmol) and CsF 00.007 g,
0.05 mmol) in DME 01 ml) was added at rt under argon
CF3TMS 02.4 ml, 1.2 mmol) over a period of 5 min. After
being stirred for 0.5 h, the reaction was quenched with 3 M
HCl. Work-up similar to that noted for 1 gave an oily
residue, which was puri®ed by preparative TLC
0AcOEt:hexane ˆ 2:3) to afford 5 00.134 g, 39%) as a
colorless oil; 1H NMR d 7.69, 7.28 0each 2H, d,
J ˆ 8:3 Hz), 5.91 01H, dt, J ˆ 6:3, 15.7 Hz), 5.75 01H, dd,
J ˆ 5:7, 15.7 Hz), 4.40±4.52 01H, m), 4.04 02H, d,
J ˆ 2:5 Hz), 3.85 02H, d, J ˆ 6:3 Hz), 3.17±3.30 01H, m),
2.40 03H, s), 2.03 01H, t, J ˆ 2:5 Hz); IR 3276, 2925, 2118,
‡
2120,1685, 1635 cmÀ1; MS m/z 321 0M ); high-resolution
‡
mass m/z calcd for C16H19NO4S 0M ) 321.1035, found:
321.1030.
‡
1680 cmÀ1; MS m/z 347 0M ); high-resolution mass m/z
‡
calcd for C15H16F3NO3S 0M ) 347.0803, found: 347.0803.
4.7. .2E)-N-.3-formyl-2-propenyl)-N-.2-
propynyl)tosylamide .37)
4.10. .2E)-N-.5,5,5-trifluoro-4-hydroxy-4-methyl-2-
pentenyl)-N-.2-propynyl)tosylamide .6)
To a solution of 36 00.647 g, 2.0 mmol) in toluene 010 ml)
was added at À788C DIBAH 06.5 ml, 6.5 mmol) over a
period of 10 min. After being stirred for 0.5 h, the reaction
was quenched with MeOH and water. The mixture was
extracted with Et2O. The organic layer was washed with
brine, dried, and evaporated under reduced pressure to give
alcohol 00.54 g, 96.0%) as an oil. The alcohol in CH2Cl2
020 ml) was treated with Dess±Martin periodinane 00.848 g,
2.0 mmol) at rt for 0.5 h. The reaction was quenched with
saturated aqueous NaHCO3. The mixture was extracted
with CH2Cl2. Work-up similar to that noted for 1 gave a
residue, which was puri®ed by column chromatography
0AcOEt:hexane ˆ 1:2) to afford 37 00.414 g, 77%) as crys-
tals; mp 68±708C; 1H NMR d 9.58 01H, d, J ˆ 7:6 Hz), 7.75,
7.34 0each 2H, d, J ˆ 8:3 Hz), 6.69 01H, dt, J ˆ 5:6,
15.8 Hz), 6.28 01H, dd, J ˆ 7:6, 15.8 Hz), 4.12 02H, d,
J ˆ 2:3 Hz), 4.11 02H, d, J ˆ 5:6 Hz), 2.45 03H, s), 2.10
To a solution of 38 00.292 g, 1.0 mmol) and CsF 00.007 g,
0.05 mmol) in DME 01 ml) was added at rt under argon
CF3TMS 02.4 ml, 1.2 mmol) over a period of 5 min. After
being stirred for 3 h, the reaction was quenched with 3 M
HCl. Work-up similar to that noted for 1 gave an oily
residue, which was puri®ed by preparative TLC
0AcOEt:hexane ˆ 2:3) to afford 6 00.075 g, 21%) as a
colorless oil; 1H NMR d 7.71, 7.31 0each 2H, d,
J ˆ 8:3 Hz), 5.90 01H, dd, J ˆ 5:6, 15.9 Hz), 5.83 01H, d,
J ˆ 15:9 Hz), 4.05 02H, d, J ˆ 2:6 Hz), 3.87 02H, d,
J ˆ 5:6 Hz), 2.42 03H, s), 2.03 01H, t, J ˆ 2:6 Hz), 1.43
‡
03H, s); IR 3475, 2925, 2124, 1598 cmÀ1; MS m/z 361 0M );
‡
high-resolution mass m/z calcd for C16H18F3NO3S 0M )
361.0966, found: 361.0959.
4.11. N-allyl-N-.4-oxo-2-butynyl)tosylamide .40)
‡
01H, t, J ˆ 2:3 Hz); MS m/z 277 0M ); high-resolution
‡
To a solution of 39 07.47 g, 30 mmol) in THF 090 ml) was
added at À788C under argon BuLi 022 ml, 33 mmol) over a
mass m/z calcd for C14H15NO3S 0M ) 277.0773, found:
277.0779.

86
M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
period of 5 min. After being stirred for 5 min, DMF 04.5 ml)
was added. Then, the mixture was stirred for 20 min and
poured into a vigorous stirred mixture of Et2O020 ml) and
10% aqueous NaH2PO3 080 ml). The mixture was extracted
with Et2O. Work-up similar to that noted for 1 gave an oily
residue, which was puri®ed by column chromatography
0AcOEt:hexane ˆ 1:3) to afford 40 03.67 g, 44%) as a pale
yellow oil; 1H NMR d 8.91 01H, s), 7.73, 7.32 0each 2H, d,
J ˆ 8:3 Hz), 5.66±5.81 01H, m), 5.26±2.30 02H, m), 4.27
02H, s), 3.83 02H, d, J ˆ 6:3 Hz), 2.43 03H, s); MS m/z 277
4.15. N-allyl-N-[3-.4-trifluoromethylphenyl)-2-
propynyl]tosylamide .7)
From 39 01.24 g, 5.0 mmol), 4-iodobenzotri¯uoride 01.0 g,
3.6 mmol), Et3N 02.8 ml, 20.2 mmol), CuI 00.024 g,
0.12 mmol), PdCl20PPh3)2 00.087 g, 0.12 mmol) in CH2Cl2
011 ml) [reaction time 2.5 h 0rt)], 7 00.777 g, 55%) was
1
obtained as crystals; mp 50±518C; H NMR d 7.77, 7.50,
7.27, 7.17 0each 2H, d, J ˆ 8:3 Hz), 5.72±5.78 01H, m),
5.26±5.30 02H, m), 4.32 02H, s), 3.89 02H, d, J ˆ 6:6 Hz),
‡
‡
‡
0M ); high-resolution mass m/z calcd for C14H15NO3S 0M )
2.34 03H, s); IR 2925, 1614 cmÀ1; MS m/z 393 0M ); high-
‡
277.0773, found: 277.0777.
resolution mass m/z calcd for C20H18F3NO2S 0M )
393.1010, found: 393.1007.
4.12. N-allyl-N-.5,5,5-trifluoro-4-hydroxy-2-
pentynyl)tosylamide .16)
4.16. N-allyl-N-[3-.4-fluorophenyl)-2-propynyl]tosylamide
.8)
To a solution of 40 00.278 g, 1.0 mmol) and TBAF 050 ml,
0.05 mmol) in THF 03 ml) was added at 08C under argon
CF3TMS 02.5 ml, 1.25 mmol) over a period of 5 min. After
being stirred for 10 min, the reaction was quenched with 1 M
HCl 03 ml). Work-up similar to that noted for 1 gave an oily
residue, which was puri®ed by preparative TLC
0AcOEt:hexane ˆ 1:2) to afford 16 00.226 g, 65%) as crys-
tals; mp 67±688C; 1H NMR d 7.73, 7.33 0each 2H, d,
J ˆ 8:3 Hz), 5.65±5.78 01H, m), 5.24±5.31 02H, m),
4.35±4.48 01H, m), 4.14 02H, s), 3.79±3.87 02H, m), 2.43
From 39 01.24 g, 5.0 mmol), 1-¯uoro-4-iodobenzene
00.6 ml, 5.0 mmol), Et3N 02.8 ml, 20.2 mmol), CuI
00.024 g, 0.12 mmol), PdCl20PPh3)2 00.087 g, 0.12 mmol)
in CH2Cl2 011 ml) [reaction time 3 h 0rt)], 8 01.422 g, 83%)
was obtained as crystals; mp 49±508C; 1H NMR d 7.77, 7.25
0each 2H, d, J ˆ 8:3 Hz), 7.05 02H, dd, J ˆ 5:4, 8.9 Hz),
6.93 02H, t, J ˆ 8:9 Hz), 5.72±5.87 01H, m), 5.24±5.28 02H,
m), 4.29 02H, s), 3.88 02H, d, J ˆ 6:6 Hz), 2.35 03H, s); IR
‡
2961, 2242, 1648, 1600 cmÀ1; MS m/z 343 0M ); high-
‡
‡
03H, s); IR 3500, 2241 cmÀ1; MS m/z 347 0M ); high-
resolution mass m/z calcd for C19H18FNO2S 0M ) 343.1043,
found: 343.1045.
‡
resolution mass m/z calcd for C15H16F3NO3S 0M )
347.0803, found: 347.0813.
4.17. N-allyl-N-[3-.pentafluorophenyl)-2-
propynyl]tosylamide .9)
4.13. N-allyl-N-.5,5,5-trifluoro-4-oxo-2-
pentynyl)tosylamide .10)
From 39 00.746 g, 3.0 mmol), penta¯uoroiodobenzene
00.882 g, 3.0 mmol), Et3N 03 ml, 21.6 mmol), CuI 00.015 g,
0.077 mmol), PdCl20PPh3)2 00.060 g, 0.085 mmol) in
CH2Cl2 03 ml) [reaction time 1 h 0408C)], 9 00.093 g, 8%)
was obtained as crystals; mp 74±758C; 1H NMR d 7.73, 7.24
0each 2H, d, J ˆ 8:3 Hz), 5.70±5.85 01H, m), 5.25±5.36 02H,
m), 4.37 02H, s), 3.86 02H, d, J ˆ 6:3 Hz), 2.32 03H, s); IR
To a solution of 16 00.226 g, 0.65 mmol) in CH2Cl2
010 ml) was added Dess±Martin periodinane 00.347 g,
0.82 mmol). After being stirred for 0.5 h, the reaction was
quenched with 10% aqueous Na2S2O3. The mixture was
extracted with CH2Cl2. Work-up similar to that noted for 1
gave a residue, which was puri®ed by column chromato-
graphy 0AcOEt:hexane ˆ 1:3) to afford 10 00.201 g, 90%)
as a colorless oil; 1H NMR d 7.71, 7.32 0each 2H, d,
J ˆ 8:3 Hz), 5.70±5.80 01H, m), 5.27±5.34 02H, m), 4.35
02H, s), 3.84 02H, d, J ˆ 6:6 Hz), 2.4103H, s); IR 3500,
‡
2247, 1597, 1502 cmÀ1; MS m/z 415 0M ); high-resolution
‡
mass m/z calcd for C19H14F5NO2S 0M ) 415.0665, found:
415.0657.
‡
2241 cmÀ1; MS m/z 345 0M ); high-resolution mass m/z
4.18. Dimethyl 2-allyl-2-[3-.4-trifluoromethylphenyl)-2-
propynyl]malonate .11)
‡
calcd for C15H14F3NO3S 0M ) 345.0643, found: 345.0645.
4.14. General procedure for palladium-catalyzed
coupling of alkynes with fluoroiodobenzenes
.7±9, 11±13)
From 41 00.630 g, 3.0 mmol), 4-iodobenzotri¯uoride
00.845 g, 3.0 mmol), Et3N 01.6 ml, 11.5 mmol), CuI
00.014 g, 0.076 mmol), PdCl20PPh3)2 00.052 g, 0.075 mmol)
in CH2Cl2 08 ml) [reaction time 0.5 h 0rt)], 11 00.847 g,
80%) was obtained as a colorless oil; 1H NMR d 7.53, 7.46
0each 2H, d, J ˆ 8:2 Hz), 5.59±5.74 01H, m), 5.14±5.23 02H,
m), 3.76 06H, s), 3.03 02H, s), 2.86 02H, d, J ˆ 7:3 Hz); IR
A mixture of acetylene 039 or 41), ¯uoroiodobenzene,
Et3N, CuI, and PdCl20PPh3)2 in CH2Cl2 was stirred under
argon. After the precipitate was ®ltered, the ®ltrate was
evaporated under reduced to give a residue, which was
puri®ed by column chromatography 0AcOEt:hexane ˆ
1:5) to afford ¯uoro-containing acetylenes.
‡
2955, 1739, 1616, 1438 cmÀ1; MS m/z 354 0M ); high-
‡
resolution mass m/z calcd for C18H17F3O4 0M ) 354.1079,
found: 354.1083.

M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
87
4.19. Dimethyl 2-allyl-2-[3-.4-fluorophenyl)-2-
propynyl]malonate .12)
0each 2H, d, J ˆ 8:3 Hz), 7.24 02H, dd, J ˆ 5:9, 8.7 Hz),
6.98 02H, t, J ˆ 8:7 Hz), 5.62±5.70 01H, m), 5.15±5.25 03H,
m), 4.13 02H, s), 3.78 02H, d, J ˆ 6:3 Hz), 2.53 01H, brs),
‡
From 41 00.630 g, 3.0 mmol), 1-¯uoro-4-iodobenzene
00.678 g, 3.0 mmol), Et3N 01.6 ml, 11.5 mmol), CuI
00.014 g, 0.076 mmol), PdCl20PPh3)2 00.052 g, 0.075 mmol)
in CH2Cl2 08 ml) [reaction time 0.5 h 0rt)], 12 00.664 g,
73%) was obtained as a colorless oil; 1H NMR d 7.33 02H,
dd, J ˆ 5:4, 8.7 Hz), 6.96 02H, t, J ˆ 8:7 Hz), 5.59±5.75
01H, m), 5.12±5.22 02H, m), 3.74 06H, s), 2.99 02H, s), 2.85
02H, d, J ˆ 7:3 Hz); IR 2954, 1738, 1602, 1508 cmÀ1; MS
2.33 03H, s); IR 3501, 1647, 1619 cmÀ1; MS m/z 373 0M );
‡
high-resolution mass m/z calcd for C20H20FNO3S 0M )
373.1111, found: 373.1129.
4.23. General procedures for Pauson±Khand
reaction
A mixture of enyne 01 eq) and Co20CO)8 01.1 eq) in
CH2Cl2, toluene or CH3CN was stirred at rt for 1 h. Method
A: NMO06±12 eq) was added to the reaction mixture. After
the mixture was stirred for 0.5±1 h, the precipitate was
removed by suction ®ltration through Celite 545 short
pad. Method B: the mixture was re¯uxed in toluene for
1±7 h. Puri®cation of the products obtained by both methods
A and B was carried out on preparative TLC.
‡
‡
m/z 304 0M ); high-resolution mass m/z calcd for
C17H17FO4 0M ) 304.1111, found: 304.1095.
4.20. Dimethyl 2-allyl-2-[3-.pentafluorophenyl)-2-
propynyl]malonate .13)
From 41 00.745 g, 3.0 mmol), penta¯uoroiodobenene
00.452 g, 1.54 mmol), Et3N 01.5 ml, 10.8 mmol), CuI
00.007 g, 0.037 mmol), PdCl20PPh3)2 00.029 g, 0.042 mmol)
in CH2Cl2 01.5 ml) [reaction time 1 h 0408C)], 13 00.044 g,
4.24. 2-Tosyl-2,3,3a,4-tetrahydro-1H-cyclopenta[c]pyrrol-
5-one .19)
1
8%) was obtained as a colorless oil; H NMR d 5.57±5.72
01H, m), 5.15±5.24 02H, m), 3.77 06H, s), 3.10 02H, s), 2.85
Mp 142±1448C 0[31] 142±1458C); 1H NMR d 7.73, 7.35
0each 2H, d, J ˆ 7:9 Hz), 5.99 01H, s), 4.34, 4.03 0each 1H,
d, J ˆ 16:5 Hz), 4.04 01H, t, J ˆ 8:4 Hz), 3.09±3.19 01H,
m), 2.55±2.66 02H, m), 2.44 03H, s), 2.06 01H, dd, J ˆ 3:6,
17.8 Hz); 13C NMR d 207.8, 179.1, 144.4, 133.6, 130.3,
127.6, 126.3, 52.6, 47.9, 44.1, 40.0, 21.7; IR 1711, 1650,
02H, d, J ˆ 7:6 Hz); IR 2957, 2252, 1741, 1521 cmÀ1; MS
‡
m/z 376 0M ); high-resolution mass m/z calcd for
C17H13F5O4 0M ) 376.0734, found: 376.0735.
‡
4.21. N-allyl-N-[4-.4-trifluoromethylphenyl)-4-hydroxy-2-
butynyl]tosylamide .14)
‡
1597 cmÀ1; MS m/z 277 0M ); high-resolution mass m/z
‡
calcd for C14H15NO3S 0M ) 277.0773, found: 277.0770.
To a solution of 39 01.245 g, 5.0 mmol) in THF 015 ml)
was added at À788C under argon BuLi 03.6 ml, 5.4 mmol)
over a period of 5 min. After being stirred for 5 min, 4-
tri¯uoromethylbenzaldehyde 00.9 ml, 6.6 mmol) was added
and the mixture was stirred for 1 h. The reaction was
quenched with water. Work-up similar to that noted for 1
gave an oily residue, which was puri®ed by column chro-
matography 0AcOEt:hexane ˆ 1:3 then 1:1) to afford 14
4.25. .3aRÃ, 4RÃ)-4-trifluoromethyl-2-tosyl-2,3,3a,4-
tetrahydro-1H-cyclopenta[c]pyrrol-5-one .20)
Mp 145±1468C; 1H NMR d 7.74, 7.37 0each 2H, d,
J ˆ 8:3 Hz), 6.07 01H, s), 4.40, 4.08 0each 1H, d,
J ˆ 17:2 Hz), 4.10 01H, dd, J ˆ 10:8, 18.3 Hz), 3.25±
2.40 01H, m), 2.85 01H, dq, J ˆ 4:8, 9.4 Hz), 2.76 01H,
dd, J ˆ 9:6, 10.8 Hz), 2.45 03H, s); 13C NMR d 197.2, 176.7,
144.5, 133.2, 130.1, 127.5, 125.4, 53.8, 51.3, 47.5, 45.1,
45.0, 21.6; IR 1715, 1644, 1597 cmÀ1; MS m/z 345 0M );
high-resolution mass m/z calcd for C15H14F3NO3S 0M )
345.0646, found: 345.0643.
1
02.030 g, 96%) as crystals; mp 59±608C; H NMR d 7.69,
7.57, 7.41, 7.20 0each 2H, d, J ˆ 8:3 Hz), 5.58±5.77 01H,
m), 5.19±5.25 03H, m), 4.15 02H, d, J ˆ 1:7 Hz), 3.79 02H,
d, J ˆ 6:6 Hz), 2.64 01H, brs), 2.33 03H, s); IR 3491, 1603,
‡
‡
‡
1508 cmÀ1; MS m/z 423 0M ); high-resolution mass m/z
‡
calcd for C21H20F3NO3S 0M ) 423.1116, found: 423.1109.
4.26. .3aRÃ, 4SÃ)-4-.4-fluorophenyl)-2-tosyl-2,3,3a,4-
tetrahydro-1H-cyclopenta[c]pyrrol-5-one .21)
4.22. N-allyl-N-[4-.4-fluorophenyl)-4-hydroxy-2-
butynyl]tosylamide .15)
Mp 178±1808C; 1H NMR d 7.74, 7.36 0each 2H, d,
J ˆ 8:3 Hz), 7.02±7.11 04H, m), 6.08 01H, s), 4.41, 4.09
0each 1H, d, J ˆ 17 Hz), 4.07 01H, t, J ˆ 9 Hz), 3.23±3.37
01H, m), 3.23 01H, d, J ˆ 4:3 Hz), 2.80 01H, dd, J ˆ 9,
10.7 Hz), 2.45 03H, s); 13C NMR d 176.5, 144.3, 132.2,
130.0, 129.8, 129.7, 127.5, 124.7, 116.0, 115.7, 57.4, 52.5,
52.1, 50.9, 47.7, 21.6; IR 1704, 1650, 1598 cmÀ1; MS m/z
To a solution of 39 01.245 g, 5.0 mmol) in THF 015 ml)
was added at À788C under argon BuLi 03.6 ml, 5.4 mmol)
over a period of 5 min. After being stirred for 5 min, 4-
¯uorobenzaldehyde 00.7 ml, 6.5 mmol) was added and the
mixture was stirred for 1 h. Similar work-up as described
above gave an oily residue, which was puri®ed by column
chromatography 0AcOEt:hexane ˆ 1:3 then 1:1) to afford
‡
371 0M ); high-resolution mass m/z calcd for C20H18FNO3S
‡
1
15 01.687 g, 91%) as a colorless oil; H NMR d 7.58, 7.19
0M ) 371.0992, found: 371.0997.

88
M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
4.27. 4-.2,2,2-Trifluoro-1-hydroxyethyl)-2-tosyl-2,3,3a,4-
tetrahydro-1H-cyclopenta[c]pyrrol-5-one .22)
4.31. 6-.Pentafluorophenyl)-2-tosyl-2,3,3a,4-tetrahydro-
1H-cyclopenta[c]pyrrol-5-one .26)
Obtained as an inseparable mixture of diastereomers; mp
118±1278C; 1H NMR d 7.72, 7.36 0each 2H, d, J ˆ 8:3 Hz),
6.01 01H, s), 4.51±4.60 01H, m), 4.32, 4.07 0each 1H, d,
J ˆ 16:8 Hz), 3.97 01H, t, J ˆ 9:3 Hz), 3.45±3.55 01H, m),
2.68±2.75 01H, m), 2.42 03H, s), 2.33 01H, dd, J ˆ 1:3,
3 Hz); 13C NMR d 205.5, 180.0, 144.2, 133.3, 130.0, 127.4,
124.4, 122.9, 66.1, 52.5, 51.6, 47.8, 43.6, 21.5; IR 3432,
Mp 64±658C; 1H NMR d 7.71, 7.34 0each 2H, d,
J ˆ 8:1 Hz), 4.36, 4.02 0each 1H, d, J ˆ 17:2 Hz), 4.12
01H, t, J ˆ 8:6 Hz), 3.22±3.40 01H, m), 2.68±2.89 02H, m),
2.43 03H, s), 2.30 01H, dd, J ˆ 3:3, 18.2 Hz); 13C NMR d
201.9, 178.3, 146.1, 144.4, 143.8, 139.7, 135.4, 133.5,
130.1, 127.4, 125.0, 52.3, 47.8, 43.1, 39.9, 21.6; IR 1726,
‡
1686, 1652, 1597 cmÀ1; MS m/z 443 0M ); high-resolution
‡
‡
1712, 1649, 1597 cmÀ1; MS m/z 375 0M ); high-resolution
mass m/z calcd for C20H14F5NO3S 0M ) 443.0615, found:
443.0623.
‡
mass m/z calcd for C16H16F3NO4S 0M ) 375.0752, found:
375.0742.
4.32. Dimethyl 6-.4-trifluoromethylphenyl)-5-oxo-
3,3a,4,5-tetrahydro-1H-pentalene-2,2-dicarboxylate .28)
4.28. 4-.2,2,2-Trifluoro-1-hydroxy-1-methylethyl)-2-tosyl-
2,3,3a,4-tetrahydro-1H-cyclopenta[c]pyrrol-5-one .23)
Oil; 1H NMR d 7.69, 7.65 0each 2H, d, J ˆ 8:9 Hz), 3.84,
3.73 0each 3H, s), 3.69, 3.31 0each 1H, d, J ˆ 19:5 Hz),
3.08±3.25 01H, m), 2.81±2.93 02H, m), 2.33 01H, dd,
J ˆ 3:5, 18 Hz), 1.73 01H, t, J ˆ 12:6 Hz); 13C NMR d
206.3, 180.6, 171.8, 170.9, 134.3, 129.9, 128.6, 125.3, 61.0,
53.3, 53.1, 43.1, 42.4, 38.6, 35.9; IR 2957, 1735, 1698,
Obtained as an inseparable mixture of diastereomers; mp
104±1128C; 1H NMR d 7.73, 7.36 0each 2H, d, J ˆ 8:3 Hz),
6.02 01H, s), 4.36, 4.07 0each 1H, d, J ˆ 17:2 Hz), 3.20±3.35
02H, m), 2.63±2.76 01H, m), 2.44 03H, s), 2.27 01H, d,
J ˆ 2:3 Hz), 1.53 03H, s); 13C NMR d 206.3, 178.2, 144.4,
133.3, 130.0, 127.5, 127.4, 125.1, 74.0, 56.0, 52.2, 47.6,
46.0, 45.4, 21.6; IR 3504, 1692, 1653, 1597 cmÀ1; MS m/z
‡
1636 cmÀ1; MS m/z 382 0M ); high-resolution mass m/z
‡
calcd for C19H17F3O5 0M ) 382.1028, found: 382.1018.
‡
389 0M ); high-resolution mass m/z calcd for C17H18F3O4S
‡
0M ) 389.0908, found: 389.0907.
4.33. Dimethyl 6-.4-fluorophenyl)-5-oxo-3,3a,4,5-
tetrahydro-1H-pentalene-2,2-dicarboxylate .29)
4.29. 6-.4-Trifluoromethylphenyl)-2-tosyl-2,3,3a,4-
tetrahydro-1H-cyclopenta[c]pyrrol-5-one .24)
Mp 124±1258C; 1H NMR d 7.53 02H, dd, J ˆ 5:4,
8.7 Hz), 7.06 02H, d, J ˆ 8:7 Hz), 3.80, 3.69 0each 3H,
s), 3.61, 3.25 0each 1H, d, J ˆ 19:1 Hz), 3.06±3.20 01H,
m), 2.74±2.87 02H, m), 2.26 01H, dd, J ˆ 3:2, 18.2 Hz), 1.73
01H, t, J ˆ 12:7 Hz); 13C NMR d 206.8, 178.3, 171.8, 171.0,
164.2, 160.6, 134.4, 130.1, 129.6, 115.5, 115.2, 61.1, 53.3,
53.0, 42.8, 42.2, 38.7, 35.9; IR 1742, 1703, 1633, 1601,
Mp 183±1848C; 1H NMR d 7.74, 7.33 0each 2H, d,
J ˆ 8:3 Hz), 7.67, 7.60 0each 2H, d, J ˆ 8:2 Hz), 4.68,
4.09 0each 1H, d, J ˆ 15:2 Hz), 4.11 01H, dd, J ˆ 6:5,
10.9 Hz), 3.18±3.32 01H, m), 2.84 01H, dd, J ˆ 6:6,
17.9 Hz), 2.67 01H, dd, J ˆ 9:6, 10.9 Hz), 2.42 03H, s),
2.30 01H, dd, J ˆ 3:6, 17.9 Hz); 13C NMR d 204.8, 174.1,
144.1, 134.8, 133.5, 133.3, 130.3, 130.0, 128.4, 127.3,
125.7, 125.5, 51.8, 48.2, 42.1, 40.5, 21.4; IR 1701, 1638,
‡
1508 cmÀ1; MS m/z 332 0M ); high-resolution mass m/z
‡
calcd for C18H17FO5 0M ) 332.1060, found: 332.1053.
‡
1617, 1600 cmÀ1; MS m/z 421 0M ); high-resolution mass
4.34. Dimethyl 6-.pentafluorophenyl)-5-oxo-3,3a,4,5-
tetrahydro-1H-pentalene-2,2-dicarboxylate .30)
‡
m/z calcd for C21H18F3NO3S 0M ) 421.0960, found:
421.0966.
Mp 1148C; 1H NMR d 3.80, 3.73 0each 3H, s), 3.38, 3.16
0each 1H, d, J ˆ 19:4 Hz), 3.20±3.37 01H, m), 2.93 01H, dd,
J ˆ 8, 12.8 Hz), 2.83 01H, dd, J ˆ 6:3, 18 Hz), 2.34 01H, dd,
J ˆ 3:2, 18 Hz), 1.83 01H, t, J ˆ 12:8 Hz); 13C NMR d
203.6, 184.9, 171.5, 170.7, 142.5, 139.5, 135.9, 124.4, 60.4,
53.4, 53.2, 41.9, 39.0, 35.4; IR 1746, 1719, 1672, 1653,
4.30. 6-.4-Fluorophenyl)-2-tosyl-2,3,3a,4-tetrahydro-1H-
cyclopenta[c]pyrrol-5-one .25)
Mp 188±1898C; 1H NMR d 7.73, 7.32 0each 2H, d,
J ˆ 8:3 Hz), 7.47 02H, dd, J ˆ 5:4, 8.6 Hz), 7.10 02H, t,
J ˆ 8:6 Hz), 4.61, 4.06 0each 1H, d, J ˆ 16:8 Hz), 4.09 01H,
dd, J ˆ 6:4, 11.1 Hz), 3.12±3.27 01H, m), 2.79 01H, dd,
J ˆ 6:4, 18 Hz), 2.62 01H, dd, J ˆ 9:4, 11.1 Hz), 2.41 03H,
s), 2.25 01H, dd, J ˆ 3:6, 18 Hz); 13C NMR d 205.3,
171.6, 144.0, 134.9, 133.6, 130.1, 130.0, 127.3, 115.8,
115.5, 51.9, 48.2, 41.8, 40.5, 21.5; IR 1700, 1638, 1594,
‡
1523, 1501 cmÀ1; MS m/z 404 0M ); high-resolution mass
‡
m/z calcd for C18H13F5O5 0M ) 404.0683, found: 404.0696.
4.35. 6-[.4-Trifluoromethylphenyl)-a-hydroxymethyl]-2-
tosyl-2,3,3a,4-tetrahydro-1H-cyclopenta[c]pyrrol-5-one
.31L, H)
‡
1508 cmÀ1; MS m/z 371 0M ); high-resolution mass
‡
m/z calcd for C20H18FNO3S 0M ) 371.0991, found:
371.0985.
31L; mp 146±1488C; 1H NMR d 7.69, 7.35 0each 2H, d,
J ˆ 8:3 Hz), 7.57, 7.48 0each 2H, d, J ˆ 7:9 Hz), 5.56 01H,

M. Ishizaki et al. / Journal of Fluorine Chemistry 111 .2001) 81±90
89
s), 4.26, 4.16 0each 1H, d, J ˆ 17:6 Hz), 3.97 01H, t,
J ˆ 8:6 Hz), 2.97±3.20 02H, m), 2.52±2.62 02H, m), 2.44
03H, s), 2.10 01H, dd, J ˆ 3:5, 18 Hz); 13C NMR d 206.8,
173.7, 146.1, 144.4, 138.9, 133.4, 130.1, 129.9, 127.5,
126.4, 125.5, 68.2, 52.0, 49.2, 48.7, 42.9, 39.4, 21.6; IR
178.2, 144.2, 144.1, 132.9, 132.5, 132.4, 131.4, 129.8,
127.1, 64.0, 51.8, 51.5, 42.8, 42.6, 39.4, 38.7, 21.1; IR
‡
3447, 1713, 1680, 1596 cmÀ1; MS m/z 375 0M ); high-
‡
resolution mass m/z calcd for C16H16F3NO4S 0M )
375.0752, found: 375.0747.
‡
3468, 1704, 1672, 1619 cmÀ1; MS m/z 451 0M ); high-
‡
resolution mass m/z calcd for C22H20F3NO4S 0M )
451.1065, found: 451.1071. 31H; mp 188±1908C; 1H
NMR d 7.64, 7.34 0each 2H, d, J ˆ 8:2 Hz), 7.50, 7.36
0each 2H, d, J ˆ 7:9 Hz), 5.55 01H, s), 4.29, 3.83 0each 1H,
d, J ˆ 17:5 Hz), 3.96 01H, t, J ˆ 8:7 Hz), 3.30±3.42 01H,
m), 3.05±3.10 01H, m), 2.61 01H, dd, J ˆ 6:4, 18 Hz), 2.45
03H, s), 2.42 01H, dd, J ˆ 8:7, 11.2 Hz), 2.01 01H, dd,
J ˆ 3:5, 18 Hz); 13C NMR d 206.6, 173.3, 145.6, 144.5,
139.7, 132.7, 130.2, 130.1, 127.6, 126.4, 125.6, 67.7, 52.2,
49.2, 47.6, 42.5, 39.7, 21.5; IR 3422, 1704, 1674, 1618,
Acknowledgements
The authors are grateful to Mrs. F. Hasegawa of this
faculty for her mass spectral measurement.
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‡
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