Heptadecafluorooctanesulfonic acid (C8F17SO3H) catalyzed intramolecular hydroamination of olefinic sulfonamides in fluorous biphase system (FBS)

Article abstract of DOI:10.1016/j.jfluchem.2006.09.012

A practical, efficient, and environmentally benign intramolecular hydroamination of olefinic sulfonamides was carried out in fluorous biphase system (FBS) using commercially available heptadecafluorooctanesulfonic acid (C₈F₁₇SO₃

Full text of DOI:10.1016/j.jfluchem.2006.09.012

Journal of Fluorine Chemistry 128 (2007) 40–45
www.elsevier.com/locate/fluor
Heptadecafluorooctanesulfonic acid (C8F17SO3H) catalyzed
intramolecular hydroamination of olefinic sulfonamides in
fluorous biphase system (FBS)
*
Yan Yin, Gang Zhao
Laboratory of Modern Synthetic Organic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 FengLin Lu, Shanghai 200032, China
Received 22 August 2006; received in revised form 15 September 2006; accepted 16 September 2006
Available online 22 September 2006
Abstract
A practical, efficient, and environmentally benign intramolecular hydroamination of olefinic sulfonamides was carried out in fluorous biphase
system (FBS) using commercially available heptadecafluorooctanesulfonic acid (C8F17SO3H) as a catalyst and perfluorodecaline (C10F18, cis- and
trans- mixture) as a fluorous solvent to produce the corresponding cyclic products in good yields. The Brønsted acid of C8F17SO3H is easily
recovered and recycled at least five times.
# 2006 Elsevier B.V. All rights reserved.
Keywords: Hydroamination; Fluorous biphase system; Brønsted acid; Cyclization; Heptadecafluorooctanesulfonic acid
1. Introduction
superacid (C8F17SO3H) could efficiently catalyze the intramo-
lecular hydroamination of olefinic sulfonamines in the fluorous
´
biphase system (FBS), which was reported by Hovath and
The nitrogen-containing heterocycles (e.g., pyrrolidines,
piperidines, indolines, and quinolines) are found in a lot of
natural products and designed compounds with various
biological activities [1]. As a consequence, much attention
has been paid to the synthesis of these molecules. In general, the
direct intramolecular hydroamination reaction of unsaturated
amines through the addition of an N–H bond across a carbon–
carbon multiple bonds, offers an efficient, atom-economical
and straightforward route to nitrogen-containing molecules [2].
Various approaches catalyzed by alkali metals [3], transition
metals [4], organo-f-element metal complexes [5] and the
Brønsted acid [6], have been extensively studied for this
seemingly simple but challenging transformation. In a previous
research, we described the use of a catalytic amount of
superacid of trifluoromethane-sulfonic acid (TfOH) to carry out
the intramolecular hydroamination of N-arylsulfonyl-2-allyla-
nilines to produce indolines or quinoline [7]. In a continuation
of our research, we found that the recoverable perfluorous
´
Rabai in 1994 [8], bearing some potential advantages, such as
simplification of work-up, easy separation of product, and reuse
of the catalyst. This kind of fluorous technique has been utilized
for a wide variety of reactions: such as oxidation [9], reduction
[10], hydroboration [11], epoxidation [12], carbon–carbon
bond forming reactions [13] and so on. Herein, we wish to
report the results of this protocol for intramolecular hydro-
amination of unactivated olefines.
2. Results and discussion
In a preliminary experiment, intramolecular hydroamina-
tion of N-tosyl-2-allylaniline (1a) was performed in the
presence of a catalytic amount of perfluorinated acid
(C8F17SO3H) in the fluorous biphase system, which toluene
and hexane were used as the solvents of organic phase, and
perfluorodecalin (C10F18, cis- and trans- mixture) as the
fluorous solvent. We observed that the C8F17SO3H showed
good solubility in the fluorous solvent and poor solubility in the
mixture of organic solvents. Upon heating up to 95 8C, the
organic phase was miscible with the fluorous phase and the
* Corresponding author. Fax: +86 21 64166128.
E-mail address: Zhaog@mail.sioc.ac.cn (G. Zhao).
0022-1139/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2006.09.012

Y. Yin, G. Zhao / Journal of Fluorine Chemistry 128 (2007) 40–45
41
Table 1
Effect of nitrogen protecting group on the hydroamination
Table 2
Effect of different substituents of phenyl ring on the reaction
Entry
PG
Substrate
Time (h)
Yield of 2 (%)a
Entry
R
Substrate
Time (h)
Product (2)
Yield (%)a
1
2
3
4
5
6
7
Ts
1a
1b
1c
1d
1e
1f
1
1
95
1
2
3
4
5
6
CH3O
CH3
Br
1h
1i
1j
1k
1l
1m
0.5
1
2h
2i
2j
2k
2l
2m
94
95
91
91
90
87
Ms
88
Ns
1
93
2
m-Ns
p-Ns
PhCO
H
1
91
Cl
2
1
92
F
2.5
5
1
Trace
0
NO2
1g
24
Experment were performed on a 0.5 mmol scale: 1 (0.5 mmol), C8F17SO3H
(5 mol%), perfluorodecalin (1 mL), toluene (1 mL) and hexane (0.33 mL).
Experment were performed on a 0.5 mol scale: 1 (0.5 mmol), C8F17SO3H
(5 mmol%), perfluorodecalin (1 mL), toluene (1 mL) and hexane (0.33 mL).
a
Isolated yield.
a
Isolated yield.
reaction mixture became homogenous. The resulting mixture
continued to reflux up to the completion of the reaction, the
corresponding product N-tosyl-2-methylindoline (2a) was
isolated in 95% yield in the presence of 5 mol% C8F17SO3H
(Table 1, entry 1). The reduction of the catalyst loading
(2 mol%) led to the lower yield (50%) in the same reaction
conditions.
density of the aromatic ring, and the substrate is not prone to
protonation.
Then, we extended the cyclization to other tosylated amino
olefins using C8F17SO3H (5 mol%) in FBS. As outlined in
Table 3. Allylic tosylamide (1n) and homoallylic tosylamide
(1o-p) did not undergo any reactions (Table 3, entries 1–3). We
assume that the three-member or four-member ring is
particularly disfavored to be formed due to their rigidity.
Other acyclic substrates of tosylated g-amino olefins (1q and
1r) formed the five-member ring products through Markovni-
kov addition in high yields (Table 3, entries 4 and 5). In the
cases of (1s–v) with an internal disubstituted double bond, the
cyclization reaction was completely regiospecific through the
benzyilic cation intermediate (Table 3, entries 6–9). Terminal
monosubstituted olefins such as 1w also was cyclized to afford
a mixture of five- and six-member ring products in overall 95%
yield (Table 3 entry 10).
To elucidate the influence of the electronic properties of the
different protecting groups of the nitrogen on the reaction, a
series of N-protected-2-allylanilines (1a–f) were examined. The
results are summarized in Scheme 1 and Table 1. After screening
1a–e, it was found that all sulfonamides gave the cyclization
products in good yields (Table 1, entries 1–5). N-Benzoyl-2-
allyl-aniline (1f) gave only trace amount of cyclized product at
refluxing in 1 h (Table 1, entry 6). While 2-allyl-aniline (1g)
underwent this transformation, the starting material 1g was not
consumed at all even after 24 h (Table 1, entry 7). It seemed to be
that the high Lewis basicity of free amine inhibited the reaction.
But treated with excess acid (>1.0 equiv.), no cyclization
reaction was proceeded and the superacid-promoted reaction
underwentbyotherpathways[14]. Togaininsightontheeffectof
the electron density of the phenyl ring of the aromatic amine,
various N-tosyl-2-allylanilines bearing different substituents at
the para position on the phenyl ring were readily prepared by the
N-allylaniline Claisen rearrangements [1a,15] followed by
sulfonylation with p-toluenesulfonyl chloride (TsCl). Under
the above optimized reaction conditions, the different para
substituted N-tosyl-2-allylanilines were transferred to substi-
tuted indolines in good to high yields, through a 5-exo-trig
cyclization route favored by Baldwin’s rules [16], as summarized
in Scheme 2 and Table 2. The electron density of the phenyl ring
had little effect on the reaction yields, but the aromatic amines
with electron-withdrawing groups required longer reaction times
than the electron-rich aromatic amines (Table 2, entries 1–5). It
took the longest reaction time to finish the reaction of the very
electron deficient alkene (1m) (Table 2, entry 6). It was attributed
that the electron-withdrawing group decreased the electron
We further investigated the stereochemistry of the cycliza-
tion of the tosylated amino alkenes of 1x and 1y bearing
stereocenters in the tether, which were prepared from styrene
and b-methylstyrene [17]. Under the same reaction conditions,
the racemic phenyl-substituted substrate 1y cleanly gave the
desired pyrrolidine as trans-/cis- mixture (91:9, determined by
1H NMR) in 92% yield after 1 h with 5 mol% C8F17SO3H. In a
case of racemic substrate 1y, the 2,3,5-trisubstituted pyrrolidine
was producded as a sole isomer in 96% yield. The trans-isomer
was obtained predominantly to indicate that the diastereos-
electivity favored the thermodynamically more stable isomer
(Scheme 3) and the stereochemistry is determined by 2D 1H–1H
NOESY (see Supporting material).
Finally, recyclable peformance of C8F17SO3H was also
investigated using 1a as a substrate (Scheme 4 and Table 4).
The fluorous catalytic phase was directly reused in the next
reaction by combining with another mixture of reactants at least
five times without loss of activity.
In conclusion, we report a novel catalytic alternative for the
cyclization of olefinic sulfonamides to nitrogen-containing
Scheme 1.
Scheme 2.

42
Y. Yin, G. Zhao / Journal of Fluorine Chemistry 128 (2007) 40–45
Scheme 3.
3. Experimental
General: 1H and 13C NMR spectra were recorded on a
Bruker DPX 300 MHz spectrometer (300 and 75 MHz,
respectively) with TMS as an internal standard. Coupling
constants are reported in Hertz (Hz). All 13C NMR spectra were
proton decoupled. Mass spectral analyzed was measured on a
HP-5989. HRMS (EI) was measured on a Finnigan MA+. IR
was measured on Perkin 983. Elemental analysis was
determined on an Italian Carlo-Erba 110. The melting points
were measure on a Melting point SGW X-4. All the products
were purified by column chromatography on silica gel with
ethyl acetate–hexane in an appropriate ratio as the eluent.
Spectroscopic data and combustion or HRMS analyses are
reported for all new compounds.
Scheme 4.
heterocycles in good to high yields, using a catalytic amount of
commercially available C8F17SO3H as a catalyst. And this
fluorous biphase system (FBS) approach offers an easy work-up
procedure and good to high yield for the cyclization product
under mild reaction conditions.
Table 3
C8F17SO3H catalyzed the cyclization reaction of tosylated amino olefins
Entry
1
Substrate
Product
Yield (%)a
b
–
3.1. General procedure of C8F17SO3H-catalyzed
hydroamination of olefinic sulfonamides in FBS
b
2
3
–
b
C8F17SO3H (0.025 mmol) was added into a mixture of
substrate (0.5 mmol), dry toluene (1 mL), hexane (0.33 mL)
and perfluorodecalin (cis- and trans- mixture, 1 mL). The
reaction mixture was stirred and heated to reflux. At the end of
the reaction, the reaction mixture was cooled to room
temperature and settled down for 2 min. The mixture was
separated into two liquid phases. The upper organic layer
afforded the corresponding product by silica gel column
chromatography (hexane:AcOEt = 10:1), while the lower
fluorous phase containing the catalyst was used in subsequent
reaction.
–
4
5
6
97
94
79
7
83
8
9
91
88
95
Table 4
Recycling performance of C8F17SO3H in FBS
Run
Catalyst loading (mol%)
Time (h)
Yield (%)a
10
1
2
3
4
5
5
5
5
5
5
1
95
95
93
94
92
1
1
1
Experment were performed on a 0.5 mmol scale: 1 (0.5 mmol), C8F17SO3H
(5 mol%), perfluorodecalin (1 mL), toluene (1 mL) and hexane (0.33 mL),
reflux, 1 h.
1.5
Experment were performed on a 2.5 mmol scale: 1 (2.5 mmol), C8F17SO3H
(5 mol%), perfluorodecalin (5 mL), toluene (5 mL) and hexane (1.67 mL).
a
Isolated yield.
b
a
No desired product was observed.
Isolated yield.

Y. Yin, G. Zhao / Journal of Fluorine Chemistry 128 (2007) 40–45
43
3.2. 2-Methyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2a) [18]
IR (KBr): y 3059, 2956, 2920, 2850, 1640, 1598, 1481,
1390, 1288, 756, 701 cmÀ1
.
White solid; 95% yield; mp 63–64 8C; 1H NMR (300 MHz,
CDCl3): d 7.66–7.64 (m, 1H), 7.56–7.53 (m, 2H), 7.26–6.98 (m,
5H), 4.35 (ddq, J = 3, 6.6, 9.6 Hz, 1H), 2.89 (dd, J = 9.6,
15.9 Hz, 1H), 2.43 (dd, J = 3.0, 15.9 Hz, 1H), 2.34 (s, 3H), 1.42
(d, J = 6.6 Hz, 3H).
3.8. 5-Methoxyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2h) [20]
White solid; 94% yield; mp 76–77 8C; 1H NMR (300 MHz,
CDCl3) d 7.58–7.48 (m, 3H), 7.15 (m, 2H), 6.77–6.60 (m, 2H),
4.36–4.27 (m, 1H), 3.76 (s, 3H), 2.78–2.70 (m, 1H), 2.40–2.30
(m, 4H), 1.38 (d, J = 6.6 Hz, 3H).
IR (KBr): y 3067, 2966, 2925, 2855, 1599, 1479, 1461,
1352, 1167, 1103, 1091, 814, 756 cmÀ1
.
IR (KBr): y 3030, 2926, 2836, 1736, 1597, 1489, 1351,
1164, 1090, 1033, 813, 750, 669 cmÀ1
3.3. Methylanesulfonyl-2-methyl-2,3-dihydro-1H-indole
(2b) [19]
.
White solid; mp 58–59 8C; 88% yield; 1H NMR (300 MHz,
CDCl3): d 7.42–7.02 (m, 4H), 4.44 (ddq, J = 3.6, 6.6, 9.6 Hz,
1H), 3.45 (dd, J = 9.6, 16.2 Hz, 1H), 2.70 (dd, J = 3.6, 16.2 Hz,
1H), 2.41 (s, 3H), 1.45 (d, J = 6.6 Hz, 3H).
3.9. 5-Methyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2i) [20]
White solid; mp 64–65 8C; 96% yield; 1H NMR (300 MHz,
CDCl3) d 7.55–7.52 (m, 3H), 7.16–6.85 (m, 4H), 4.31 (ddq,
J = 2.7, 6.6, 9.6 Hz, 1H), 2.81 (dd, J = 9.6, 15.9 Hz, 1H), 2.39
(dd, J = 2.7, 15.9 Hz, 4H), 2.34 (m, 3H), 2.27 (s, 3H), 1.40 (d,
J = 6.6Hz, 3H).
IR (KBr): y 3015, 2970, 2929, 2852, 1602, 1479, 1460,
1346, 1159, 961, 767 cmÀ1
.
3.4. 2-Methyl-1-(2-nitro-benzenesulfonyl)-2,3-dihydro-1H-
indole (2c) [20]
IR (KBr): y 2957, 2924, 2853, 1597, 1486, 1349, 1164,
1090, 983, 813, 666, 614, 584, 542 cmÀ1
.
White solid; 93% yield; mp 107–108 8C; 1H NMR
(300 MHz, CDCl3) d 7.85–7.03 (m, 8H), 4.71 (m, 1H), 3.29
(m, 1H), 2.58 (m, 1H), 1.40 (d, J = 6.3Hz, 3H).
IR (KBr): y 3096, 2922, 2851, 1592, 1545, 1478, 1371,
1172, 1126, 756, 597.
3.10. 5-Bromo-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2j) [20]
White solid; 90% yield; mp 84–85 8C; 1H NMR (300 MHz,
CDCl3) d 7.53–7.51 (m, 3H), 7.33–7.30 (m, 1H), 7.20–7.17 (m,
3H), 4.33 (ddq, J = 2.4, 6.3, 9.3 Hz, 1H), 2.82 (dd, J = 9.3,
15.9 Hz, 1H), 2.42 (dd, J = 2.4, 15.9 Hz, 4H), 2.36 (s, 3H), 1.42
(d, J = 6.3 Hz, 3H).
3.5. 2-Methyl-1-(3-nitro-benzenesulfonyl)-2,3-dihydro-1H-
indole (2d) [20]
White solid; 91% yield; mp 104–105 8C; 1H NMR
(300 MHz, CDCl3) d 8.56–7.06 (m, 8H), 4.42 (ddq, J = 2.7,
6.3, 9.3 Hz, 1H), 2.94 (dd, J = 9.3, 16.2 Hz, 1H), 2.52 (dd,
J = 2.7, 16.2 Hz, 1H), 1.47 (d, J = 6.3Hz, 3H).
IR (KBr): y 2957, 2924, 2853, 1736, 1597, 1470, 1353,
1168, 1097, 814, 725, 666, 581, 540 cmÀ1
.
IR (KBr): y 3082, 2926, 1605, 1533, 1479, 1352, 1176,
1127, 762 cmÀ1
3.11. 5-Chloro-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2k) [20]
.
3.6. 2-Methyl-1-(4-nitro-benzenesulfonyl)-2,3-dihydro-1H-
indole (2e) [20]
White solid, 91% yield; mp 81–82 8C; 1H NMR (300 MHz,
CDCl3) d 7.58–7.53 (m, 3H), 7.19–7.01 (m, 4H), 4.34 (m,
1H), 2.85 (m, 1H), 2.43–2.35 (m, 4H), 1.41 (d, J = 6.6 Hz,
3H).
White solid; 92% yield; mp 137–138 8C; 1H NMR
(300 MHz, CDCl3) d 8.23 (d, J = 8.7 Hz, 2H), 7.87 (d,
J = 8.7 Hz, 2H), 7.69–7.66 (m, 1H), 7.27–7.07 (m, 3H), 4.37
(ddq, J = 2.4, 6, 9.3 Hz, 1H), 2.91 (dd, J = 9.3, 16.2 Hz, 1H),
2.50 (dd, J = 2.4, 16.2 Hz, 1H), 1.46 (d, J = 6Hz, 3H).
IR (KBr): y 3104, 2958, 2924, 2853, 1604, 1531, 1349,
IR (KBr): y 2963, 2927, 2852, 1598, 1472, 1353, 1165,
1090, 814, 666, 582 cmÀ1
.
3.12. 5-Fluoro-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2l) [20]
1309, 1171, 1087, 740 cmÀ1
.
3.7. (2-Methyl-2, 3-dihydro-indol-1-yl)-phenyl-methanone
(2f) [21]
White solid; 91% yield; mp 116–117 8C; 1H NMR
(300 MHz, CDCl3) d 7.62–7.50 (m, 3H), 7.19–7.16 (m, 2H),
6.93–6.74 (m, 2H), 4.36 (m, 1H), 2.80 (m, 1H), 2.41–2.34 (m,
4H), 1.40 (d, J = 6.6 Hz, 3H).
White solid; trace yield; mp 92–93 8C; 1H NMR (300 MHz,
CDCl3) d 7.48 (m, 5H), 7.22 (m, 2H), 7.02 (m, 2H), 4.75 (m,
1H), 3.42 (m, 1H), 2.65 (m, 1H), 1.25 (d, J = 4.8 Hz, 3H).
IR (KBr): y 2970, 2926, 2859, 1594, 1481, 1348, 1164,
1084, 668, 589 cmÀ1
.

44
Y. Yin, G. Zhao / Journal of Fluorine Chemistry 128 (2007) 40–45
3.13. 5-Nitro-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-indole
(2m) [20]
4.81–4.77 (m, 1H), 3.65–3.58 (m, 1H), 3.47–3.39 (m, 1H), 2.42
(s, 3H), 2.00–1.56 (m, 4H).
IR (KBr): y 2975, 2873, 1598, 1494, 1346, 1159, 1094, 667,
White solid; 87% yield; mp 122–123 8C; 1H NMR
(300 MHz, CDCl3) d 8.13 (m, 1H), 7.94 (m, 1H), 7.72–7.63
(m, 3H), 7.26–7.23 (m, 2H), 4.49 (ddt, J = 3.3, 6.6, 9.6 Hz, 1H),
3.12 (dd, J = 9.6, 16.2 Hz, 1H), 2.63 (dd, J = 3.3, 16.2 Hz, 1H),
2.38 (s, 3H), 1.50 (d, J = 6.6Hz, 3H).
588 cmÀ1
.
3.19. 2-Phenyl-1-(toluene-4-sulfonyl)-piperidine (2v) [22]
White solid; 88% yield; mp 136–137 8C; 1H NMR
(300 MHz, CDCl3) d 7.79–7.75 (m, 2H), 7.35–7.10 (m, 7H),
5.27 (m, 1H), 3.85 (m, 1H), 3.01 (m, 1H), 2.44 (s, 3H), 1.69–
1.30 (m, 6H).
IR (KBr): y 3089, 2970, 2927, 2852, 1712, 1598, 1518,
1338, 1166, 1074, 749, 666 cmÀ1
.
3.14. 2-Methyl-1-(toluene-4-sulfonyl)-pyrrolidine (2q)
[14]
IR (KBr): y 2940, 1449, 1337, 1155, 1103, 946, 722,
665 cmÀ1
.
White solid; 97% yield; mp 94–95 8C; 1H NMR (300 MHz,
CDCl3) d 7.71 (d, J = 8.1 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H),
3.72–3.66 (m, 1H), 3.46–3.39 (m, 1H), 3.17–3.09 (m, 1H), 2.41
(s, 3H), 1.86–1.44 (m, 4H), 1.30 (d, J = 6.3 Hz, 3H).
3.20. 2-Ethyl-1-(toluene-4-sulfonyl)-pyrrolidine (2w) [23]
and 2-methyl-1-(toluene-4-sulfonyl)-piperidine (2ww) [23]
They were obtained as a mixture. Since they were difficult to
1
isolate from each other, the measurement of H NMR was
1
carried out for the mixtures. H NMR (300 MHz, CDCl3) d
IR (KBr): y 2966, 2927, 1597, 1460, 1341, 1158, 1092, 661,
.
549 cmÀ1
7.73–7.26 (m, 8H), 4.25–4.23 (m, 1H), 3.73–3.69 (m, 1H),
3.56–3.52 (m, 1H), 3.42–3.34 (m, 1H), 3.23–3.17 (m, 1H),
3.02–2.94 (m, 1H), 2.42 (s, 3 H), 2.41 (s, 3H), 1.90–1.49 (m,
12H), 1.06 (d, J = 7.2 Hz, 3H), 0.91 (t, J = 7.8 Hz, 3H).
3.15. 2-Methyl-1-(toluene-4-sulfonyl)-octahydro-indole
(2r)
White solid; 94% yield; mp 58–59 8C; 1H NMR (300 MHz,
CDCl3) d 7.75–7.71 (m, 2H), 7.32–7.25 (m, 2H), 3.83 (m, 1H),
3.63-3.50 (m, 1H), 2.42 (s, 3H), 2.27–1.05 (m, 14H).
3.21. 2-Methyl-4-phenyl-1-(toluenesulfonyl)-pyrrolidine
(2x + 2xx)
IR (KBr): y 2927, 2861, 1599, 1449, 1337, 1161, 1095,
664 cm-1; ESI calculated for C16H23NO2S [M + Na+1]
316.1344; found 316.1342. Anal. Calcd. for C16H23NO2S: C,
65.49; H, 7.90; N, 4.77; Found: C, 65.56; H, 8.00; N, 4.62.
White solid; 92% yield; mp 83–84 8C; mixture of trans-, cis-
isomers: 91:9 (1H NMR). The relative stereochemistry was
determined by NOESY-experiment. 1H NMR (300 MHz,
CDCl3) (mixture of syn and anti isomers): d 7.78 (d,
J = 8.2 Hz, 0.91 H) (anti), 7.75 (d, J = 8.2 Hz, 0.09H) (syn),
7.35 (d, J = 8.2 Hz, 0.91 H) (anti), 7.30 (m, 0.09 H) (syn), 7.25
(d, J = 7.2 Hz, 0.91H) (anti.), 7.20 (m, 0.09 H) (syn), 7.10 (d,
J = 7.2 Hz, 0.91H) (anti), 7.05 (d, J = 7.2 Hz, 0.09H), 3.95 (m,
0.09 H) (syn), 3.80 (m, 0.91 H) (anti), 3.70 (m, 0.91H) (anti),
3.55 (m, 0.09 H) (syn), 3.39 (t, J = 11.2 Hz, 0.91 H) (anti), 3.00
(t, J = 11.2 Hz, 0.09 H) (syn), 2.68 (m, 1H), 2.43 (s, 3 H), 2.32
(m, 1H), 1.85 (m, 0.09 H) (syn), 1.74 (m, 0.91 H) (anti), 1.48 (d,
J = 6.2 Hz, 2.73 H) (anti), 1.42 (d, J = 6.2 Hz, 0.27 H) (syn).
13C NMR (75 MHz, CDCl3) (mixture of syn and anti
isomers): d 18.0 (syn), 21.4 (anti), 22.5 (anti), 23.4 (syn), 39.7
(syn), 41.5 (syn), 42.1 (anti), 42.8 (anti), 55.0 (anti), 55.9 (syn),
56.9 (anti), 60.0 (syn), 126.8 (anti), 127.3 (anti), 128.5 (anti),
129.6 (anti), 132.0 (syn), 135.3 (syn), 139.6 (syn), 143.3 (syn).
3.16. 2-Phenyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
indole (2s) [20]
White solid; 79% yield; mp 101–102 8C; 1H NMR
(300 MHz, CDCl3) d 7.72–7.52 (m, 3H), 7.29–7.03 (m,
10H), 5.42 (dd, J = 2.7, 10.2 Hz, 1H), 3.26 (dd, J = 10.2,
16.2 Hz, 1H), 2.86 (dd, J = 2.7, 16.2 Hz, 1H), 2.34 (s, 3H).
IR (KBr): y 3064, 3031, 2920, 2852, 1598, 1494, 1478,
1460, 1355, 1168, 1091, 1028, 814, 756, 576 cmÀ1
.
3.17. 2-Phenyl-1-(toluene-4-sulfonyl)-1,2,3,4-tetrahydro-
quinoline (2t) [20]
White solid; 83% yield; mp 109–110 8C; 1H NMR
(300 MHz, CDCl3) d 7.89–7.86 (m, 1H), 7.44–6.94 (m,
12H), 5.35 (t, J = 7.2 Hz, 1H), 2.38 (s, 3H), 2.35–2.29 (m,
1H), 2.23–2.12 (m, 1H), 1.89–1.72 (m, 2H).
IR (KBr): y 2967, 1598, 1495, 1341, 1160, 1090 cmÀ1
ESI-LRMS: m/z 316.2 (M + 1)+.
.
Anal. Calcd. for C18H21NO2S: C, 68.54; H, 6.71; N, 4.44.
Found: C, 68.78; H, 6.50; N, 4.28.
IR (KBr): y 3062, 3029, 2948, 2844, 1599, 1486, 1454,
1347, 1164, 1090, 972, 813, 759, 660, 584, 570, 549 cmÀ1
.
3.22. (Trans,cis)-2,5-dimethyl-3-phenyl-1-
(toluenesulfonyl)-pyrrodiline (2y)
3.18. 2-Phenyl-1-(toluene-4-sulfonyl)-pyrrolidine (2u)
[22]
White solid; 96% yield; mp 120–121 8C; 1H NMR
(300 MHz, CDCl3) d 7.76 (d, J = 8.1 Hz, 2H), 7.31–7.20
(m, 5H), 7.15 (d, J = 8.1 Hz, 2H) 4.12–4.01 (m, 1H), 3.95–3.86
White solid; 91% yield; mp 102–103 8C; 1H NMR
(300 MHz, CDCl3) d 7.68–7.66 (m, 2H), 7.31–7.22 (m, 7H),

Y. Yin, G. Zhao / Journal of Fluorine Chemistry 128 (2007) 40–45
45
[5] (a) B.D. Stubbert, C.L. Stern, T.J. Marks, Organometallics 22 (2003)
4836–4838;
(m, 1H), 2.83–2.75 (m, 1H), 2.54–2.47 (m, 1H), 2.43 (s, 3H),
1.74–1.64 (m, 1H), 1.39 (d, J = 6.6 Hz, 3H), 1.29 (d, J = 6 Hz,
3H).
13C NMR (75 MHz, CDCl3) d 142.7, 141.6, 140.2, 129.5,
128.6, 127.5, 127.0, 126.9, 63.2, 56.6, 52.0, 41.8, 21.7, 21.5,
19.2.
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IR (KBr): y 2970, 2929, 1600, 1495, 1335, 1165, 1091; MS
(EI) (m/z) 329, 314, 238, 174, 155, 91 cmÀ1.
MALDI-HMRS m/z calcd. for C19H24NO2S [M + H+]:
330.1529; found: 330.1522.
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Acknowledgement
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We are grateful to National Natural Science Foundation of
China (nos. 20525208, 20532040, 20390057 and 20372072),
QT program for financial support.
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