Au(I)-catalyzed cyclization of enynes bearing an olefinic cycle

Article abstract of DOI:10.1021/jo061254r

(Chemical Equation Presented) Gold(I)-catalyzed cyclization of enynes containing an olefinic cycle has been studied. The introduction of an olefinic ring instead of a terminal alkene in enynes dramatically increased the yield of the reaction. Enynes havin

Full text of DOI:10.1021/jo061254r

Au(I)-Catalyzed Cyclization of Enynes Bearing an Olefinic Cycle
Sang Ick Lee, Soo Min Kim, Mi Ra Choi, Sun Young Kim, and Young Keun Chung*
Intelligent Textile System Research Center, Department of Chemistry, College of Natural Sciences, Seoul
National UniVersity, Seoul 151-747, Korea
Won-Sik Han and Sang Ook Kang
Department of Chemistry, Korea UniVersity, 208 Seochang, Chociwon, Chung-nam 339-700, Korea
ykchung@snu.ac.kr
ReceiVed June 19, 2006
Gold(I)-catalyzed cyclization of enynes containing an olefinic cycle has been studied. The introduction
of an olefinic ring instead of a terminal alkene in enynes dramatically increased the yield of the reaction.
Enynes having an olefinic cycle were prepared by a rhodium-catalyzed intermolecular [4 + 2] cycloaddition
of diynes with butadiene. Consecutive rhodium-catalyzed Diels-Alder/gold(I)-catalyzed cycloisomerization
reactions were integrated in a one-pot reaction.
Introduction
cycloisomerization of enynes having an olefinic cycle and
integration of the generation and cycloisomerization of enynes
bearing an olefinic cycle into a “one-pot” transformation.
Transition-metal-catalyzed cycloisomerizations of enynes
provide rapid and efficient access to a variety of cyclic structural
1
motifs with a broad range of synthetically useful applications.
Among them, the latest advances in gold(I)2 catalysis are
particularly noteworthy. For this reason, gold complexes have
recently emerged as valuable catalysts in the conversion of
Results and Discussion
For reference purposes, the yields from the cycloisomerization
of enynes obtained in our laboratory are summarized in Scheme
3
various types of enynes into a range of useful structural motifs.
1
. Interestingly, when the reaction time was lengthened, a
Under these circumstances, while we were pursuing the
improvement of the gold(I)-catalyzed enyne cycloisomerization
yields, we found that the introduction of an olefinic cycle instead
of a terminal alkene dramatically improved the yield of the
reaction. Herein, we report our results on the gold(I)-catalyzed
reductive dimerization occurred. The reductive dimerized
product (2a′) was confirmed by an X-ray study (Figure 1). We
surmised that the extra hydrogens found in 2a′ was derived from
adventitious water under our reaction conditions. When an enyne
(3e) bearing a cyclic olefin at the terminal olefin and an internal
alkyne was used, the yield of the reaction was dramatically
improved to 98% within 30 min. Moreover, no dimerization
was observed. This dramatic increase in the yield was presum-
ably in part due to the conformational restriction of the carbon-
carbon double bond in the cyclic olefin compared to that of the
CdC bond in the terminal olefin.
(
1) For recent reviews, see: (a) Hashmi, A. S. K. Appl. Catal. A: Gen.
2
005, 291, 238-246. (b) Corti, C. W.; Holliday, R. J.; Thompson, D. T.
Appl. Catal. A: Gen. 2005, 291, 253-261. (c) Hoffmann-R o¨ der, A.; Krause,
N. Org. Biomol. Chem. 2005, 3, 387-391. (d) Liu, Z. P.; Hu, P. Topics
Catal. 2004, 28, 71-78. (e) Haruta, M. Gold Bull. 2004, 37, 27-36. (f)
Hashmi, A. S. K. Gold Bull. 2004, 37, 51-65. (g) Bond, G. C. Catal. Today
2
4
002, 72, 5-9. (h) Dyker, G. Angew. Chem., Int. Ed. 2000, 39, 4237-
239.
(
2) For Pd-catalyzed reactions, see: (a) Trost, B. M.; Hashmi, A. S. K.
J. Am. Chem. Soc. 1994, 116, 2183-2184. For Au(I)-catalyzed reactions,
see: (b) Nieto-Oberhuber, C.; Mu n˜ oz, M. P.; Bu n˜ uel, E.; Nevado, C.;
C a´ rdenas, D. J.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 2402-
(3) (a) Gagosz, F. Org. Lett. 2005, 7, 4129-4132. (b) Mezailles, N.;
Ricard, L.; Gagosz, F. Org. Lett. 2005, 7, 4133-4136. (c) Mu n˜ oz, M.; Adrio,
J.; Carretero, J. C.; Echavarren, A. M. Organometallics 2005, 24, 1293-
1300. (d) Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2005, 127, 6962-
6963. (e) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc.
2004, 126, 10858-10859. (f) Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc.
2004, 126, 11806-11807. (g) Mamane, V.; Gress, T.; Krause, H.; F u¨ rstner,
A. J. Am. Chem. Soc. 2004, 126, 8654-8655.
2
406. (c) Hashmi, A. S. K.; Blanco, M. C.; Kurpejovic, E.; Frey, W.; Bats,
J. W. AdV. Synth. Catal. 2006, 348, 709-713. For PtCl2-catalyzed reactions,
see: (d) Nevado, C.; Ferrer, C.; Echavarren, A. M. Org. Lett. 2004, 6, 3191-
3
5
194. (e) Blum, J.; Berr-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60,
567-5569.
10.1021/jo061254r CCC: $33.50 © 2006 American Chemical Society
9
366
J. Org. Chem. 2006, 71, 9366-9372
Published on Web 11/15/2006

Au(I)-Catalyzed Cyclization of Enynes Bearing an Olefinic Cycle
SCHEME 1
FIGURE 1. X-ray structure of 2a′ (30% thermal ellipsoid).
7
exhibit reaction sequence selectivity. Thus, when the tandem
The steric hindrance might enable the CdC bond to partici-
pate easily in the cycloisomerization. Similar tricyclic com-
reaction was initiated, both catalysts, Rh and Au, coexisted with
the substrates. Diyne 1m (0.162 g, 0.62 mmol) and 2,3-
dimethylbutadiene (0.11 mL, 0.93 mmol) were reacted in the
presence of [Rh(NHC)(cod)Cl] (20 mg, 5 mol %), Au(PPh3)Cl
pounds bearing a cyclopropane had been reported by Trost’s,
F u¨ rstner’s, and Echavarren’s groups.2
a,c,4
They studied a plat-
inum- and gold-catalyzed cycloisomerization of enynes contain-
ing a heteroatom in the tether and a cyclic olefin. Thus, we
decided to study the gold(I)-catalyzed cycloisomerization of
enynes bearing a cyclic olefin in detail.
Enynes (3) bearing a cyclic olefin used in this study were
easily synthesized by a Diels-Alder reaction of suitable diynes
1) with 2,3-dimethylbutadiene in the presence of [Rh(NHC)-
(15 mg, 5 mol %), and AgSbF6 (30 mg, 15 mol %) in
dichloromethane at room temperature. After the reaction, 4m
was obtained in a 50% yield. The overall yield was low
compared to those of the two separate reactions combined (69%
and 99%, respectively), presumably due to the decomposition
of diynes in the presence of Au(PPh3)Cl/AgSbF6. Thus, to
improve the yield of the reaction, a one-pot tandem reaction
via a sequential addition of rhodium(I) and gold(I) catalysts was
tried. After completion of the Diels-Alder reaction of 1m (0.162
mg, 0.62 mmol) in the presence of [Rh(NHC)(cod)Cl] (20 mg,
(
(
2
cod)Cl]/AgSbF6 (NHC)N,N′-bis(2,6-diisopropropyl)imidazole-
5
-yilidene) (Table 1). Most of the Diels-Alder reactions studied
went to completion within 30 min in high yields. The reaction
time and yield were dependent upon the substituent on the
alkyne unit. Compared to those of alkyl substituents, relatively
high yields were obtained for aryl substitutents. The rhodium
does not catalyze the second cycloisomerization under the
reaction conditions.
5
mol %)/AgSbF6 (15 mg, 7 mol %), Au(PPh3)Cl (15 mg, 7
mol %) and AgSbF6 (13 mg, 7 mol %) were added, and the
whole mixture was stirred at the same temperature for 1 h.
Chromatography on a silica gel column eluting with hexane/
ethyl acetate (v/v, 3:1) gave 4m in a 66% yield. Thus, a two-
step, one-pot reaction was realized in dichloromethane in a
reasonable period of time.
Next, we screened the gold-catalyzed cycloisomerization of
various enynes (3) (Table 2). As shown in Table 2, the enynes
studied produced quite good results. Formation of the cyclo-
propanated compounds (4) was confirmed by an X-ray study
of 4i (Figure 2). However, when R1 was a cyclopropyl (entry
Scheme 2 shows that the product distributions depended on
the structure of the substrates. When an enyne (1r) with a
terminal alkyne was subjected to the reaction conditions,
polymerized compounds were obtained before a gold-catalyzed
reaction occurred. Reaction of diphenyl-substituted diyne (1s)
with the rhodium catalyst yielded an enyne (3s) in 78% yield.
However, treatment of 1s with the gold catalyst produced an
1
0), the expected product (4o) was obtained in 46% yield with
the concomitant formation of an isomerized 5,4,6-tricyclic diene
compound (5) in 48% yield. Similar gold- and platinum-
catalyzed [2 + 2] cycloaddition reactions of enynes were
6
reported by Echavarren’s and F u¨ stner’s groups. Moreover,
8a
intramolecular [3 + 2] cycloadduct, 7, in 85% yield. Diynes
when R1 was a cyclohexenyl, a 6,5,6,6-tetracyclic triene
(1t and 1u) having tethers lengthened by one carbon were also
compound (6) was obtained in 85% yield. The structures of 5
studied. Diels-Alder reaction products (3t and 3u) were
obtained in 98% and 85% yields, respectively. However, they
1
13
and 6 were confirmed by H and C NMR studies, including
HMBC and HMQC.
Next we investigated the possibility of integrating the Diels-
Alder reaction and the cycloisomerization into a “one-pot”
transformation (eq 1).
(
4) F u¨ rstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122,
6785-6786. F u¨ rstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2001,
123, 11863-11869.
(5) Lee, S. I.; Park, S. Y.; Park, J. H.; Jung, I. G.; Choi, S. Y.; Chung,
Y. K.; Lee, B. Y. J. Org. Chem. 2006, 71, 91-96.
6) (a) Nieto-Oberhuber, C.; L o´ pez, S.; Mu n˜ oz, M. P.; C a´ rdenas, D. J.;
Bu n˜ uel, E.; Nevado, C.; Echavarren, A. M. Angew. Chem., Int. Ed. 2005,
4, 6146-6148. (b) F u¨ rstner, A.; Davies, P. W.; Gress, T. J. Am. Chem.
Soc. 2005, 127, 8244-8245. (c) Trost, B. M.; Chang, V. K. Synthesis 1993,
, 824-832.
7) For recent reviews, see: (a) Wasilke, J.-C.; Obrey, S. J.; Baker, R.
(
4
8
(
T.; Bazan, G. C. Chem. ReV. 2005, 105, 1001-1020. (b) Fogg, D. E.; dos
Santos, E. N. Coord. Chem. ReV. 2004, 248, 2365-2379. (c) Lee, J. M.;
Na, Y.; Han, H.; Chang, S. Chem. Soc. ReV. 2004, 33, 302-312. (d)
Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754-3760.
In a tandem reaction, each catalyst must be compatible with
the substrates, intermediates, and other catalysts and must also
J. Org. Chem, Vol. 71, No. 25, 2006 9367

Lee et al.
TABLE 1. Rh(I)-Catalyzed Intermolecular [4 + 2] Cycloaddition
a
of Diynes
entry
X
R1
time
yield (%)b
1
2
3
4
5
6
7
8
9
1f
1g
1h
1i
1j
1k
1i
NTs
Ph
30 min
30 min
30 min
30 min
30 min
98 (3f)
85 (3g)
89 (3h)
82 (3i)
84 (3j)
86 (3k)
97 (3l)
69 (3m)
81 (3n)
68 (3o)
58 (3p)
C(CO2Me)2 Ph
NTs
NTs
NTs
NTs
NTs
p-iolyl
4-methoxyphenyl
2-bromophenyl
3,5-dimethylphenyl 30 min
naphthalene
Me
30 min
30 mn
30 min
3 h
1m NTs
1n
1o
1p
NTs
NTs
NTs
Et
FIGURE 2. X-ray structure of 4i (30% thermal ellipsoid).
1
1
0
1
c-Pr(C3H5)
cyclohexynyl
1 h
SCHEME 2
a
0
.52 mmol of substrate (0.1 M), 5 mol % of Rh-NHC, and 7 mol %
b
of AgSbF6 were used. Isolated yield.
TABLE 2. Au(I)-Catalyzed Cycloisomerization of Enynesa
entry
X
R1
time (min) yield (%)b
1
2
3
4
5
6
7
8
9
3f
NTs
Ph
30
30
30
30
30
30
30
30
30
30
99 (4f)
N/Ac
3g C(CO2Me)2 Ph
3h NTs
31 NTs
3j
3k NTs
3l NTs
3m NTs
3n NTs
3o NTs
SCHEME 3
p-tolyl
91 (4h)
85 (4i)
93 (4j)
85 (4k)
85 (4l)
99 (4m)
98 (4n)
46 (4o)
4-methoxyphenyl
2-bromophenyl
3,5-dimethylphenyl
naphthalene
Me
NTs
Et
1
0
c-Pr(C3H5)
a
0
.52 mmol of substrate (0.1 M), 5 mol % of (PPh3)AuCl, and 7 mol %
b
c
of AgSbF6 were used. Isolated yield. Polymerized products were ob-
tained.
enyne with a cyclic olefin (Scheme 3). Thus, the synthesized
diendiyne 1v was first treated with [Rh(NHC)(cod)Cl]/AgSbF6.
After reaction, the expected enyne 2v having a cyclic olefin
was isolated in 98% yield. The structure of 2v was confirmed
by an X-ray diffraction study (see the Supporting Information).
Treatment of 2v with [(PPh )Au]Cl and AgSbF afforded the
were completely inert to the cycloisomerization. Thus, the chain
length between a C-C triple bond and a C-C double bond
seems to be quite important for a successful reaction.
3
6
The above studies dealt only with an intermolecular Diels-
Alder reaction product. As an extension of the above study, we
devised an intramolecular Diels-Alder reaction to generate an
expected tetracyclic diene compound 4v in 93% yield.
Conclusion
We have developed a highly efficient gold-catalyzed cycloi-
somerization of enynes bearing a cyclic olefin. The reaction
proceed at room temperature, in contrast with that found in
reactions catalyzed by Pt(II), which require heating at 80 °C.
This catalytic process provides rapid access to highly fused
polycyclic diene compounds.
(
8) Recently, the formation of 7 was reported. (a) Lian, J.-J.; Chen, P.-
C. Ting, H.-P. Liu, R.-S. J. Am. Chem. Soc. 2006, 128, 11372-11373.
Similar reactions were reported by Echavarren’s, Gagosz’s, and Shibata’s
groups. See ref 3b. (b) Nieto-Oberhuber, C.; L o´ pez, S.; Echavarren, A. M.
J. Am. Chem. Soc. 2005, 127, 6178-6179. (c) Shibata, T.; Fujiwara, R.;
Takano, D. Synlett 2005, 2062-2066.
9368 J. Org. Chem., Vol. 71, No. 25, 2006

Au(I)-Catalyzed Cyclization of Enynes Bearing an Olefinic Cycle
Experimental Section
Hz, 11.6 Hz, 1 H), 3.92 (d, J ) 11.4 Hz, 1 H), 5.31 (d, J ) 8.3 Hz,
1
H), 5.46 (m, 1 H), 6.37 (d, J ) 8.2 Hz, 1 H), 7.32 (d, J ) 8.1
1
3
General Procedure for Rh-NHC-Catalyzed Intermolecular
Hz, 2 H), 7.67 (d, J ) 8.3 Hz, 1 H); C NMR (CDCl , 75 MHz)
3
[
4 + 2] Cycloaddition. To a flame-dried 15 mL Schlenk flask
δ 19.3, 21.7, 22.5, 23.0, 23.4, 25.2, 25.3, 26.7, 41.1, 114.8, 120.9,
122.3, 127.2, 129.9, 135.1, 138.6, 143.8; exact mass for C H N S O
1 1 2
(EI) calcd 329.1450, found 329.1451; IR (cm ) 2912 (w), 2864
(w), 1620 (s), 1530 (s).
capped with a rubber septum was injected 5 mL of dichloromethane
via syringe under N flow. Rh-NHC (13 mg, 5 mol %) and AgSbF
1
9
23
-
1
2
6
(
16 mg, 7 mol %) were added sequentially. The Rh-NHC solution
was stirred for 10 min. A diene (1.5 equiv, 1 mmol) was injected
in the flask by 1 mL syringe. A diyne (0.52 mmol) was put into
N-(Cyclohexenylmethyl)-4-methyl-N-(3-phenylprop-2-ynyl)-
1
benzenesulfonamide (3e): H NMR (CDCl
(
3
, 300 MHz) δ 1.64
2
the flask under N flow. The reaction was monitored by thin-layer
m, 4 H), 2.05 (m, 4 H), 2.33 (s, 3 H), 3.75 (s, 2 H), 4.24 (s, 2 H),
chromatography. After the reactant disappeared, solvent was
removed under reduced pressure. Flash chromatography on a silica
gel eluting with hexane and ethyl acetate (v/v, 10:1) gave the
product.
General Procedure for Au(I)-Catalyzed Cycloisomerization
of Enyne. To a flame-dried 15 mL Schlenk flask capped with a
rubber septum was injected 5 mL of dichloromethane via syringe
5
.74 (s, 1 H), 7.05 (d, J ) 6.6 Hz, 2 H), 7.26 (m, 5 H), 7.78 (d, J
13
)
8.1 Hz, 2 H); C NMR (CDCl
5.4, 26.1, 36.3, 53.2, 82.0, 85.7, 122.4, 127.8, 127.9, 128.2, 128.4,
25 1 1 2
29.6, 131.6, 131.9, 136.2, 143.4; exact mass for C23H N S O
3
, 75 MHz) δ 21.5, 22.4, 22.7,
2
1
-
1
(EI) calcd 379.1606, found 379.1601; IR (cm ) 2930 (w), 2832
(w), 2210 (m), 2128 (w), 1638 (w), 1587 (w).
1
4
e: H NMR (CDCl
3
, 300 MHz) δ 0.65 (m, 2 H), 1.02 (m, 2
under N
mg, 7 mol %) were added sequentially. The Au solution was stirred
for 10 min. A enyne (0.52 mmol) was put into the flask under N
2 3 6
flow. (PPh )AuCl (13 mg, 5 mol %) and AgSbF (16
H), 1.24 (m, 1 H), 1.66 (m, 4 H), 2.45 (s, 3 H), 2.90 (d, J ) 11.6
Hz, 1 H), 3.91 (d, J ) 11.6 Hz, 1 H), 5.19 (d, J ) 8.0 Hz, 1 H),
2
6
7
7
2
1
.24 (d, J ) 8.0 Hz, 1 H), 7.13 (d, J ) 6.8 Hz, 1 H), 7.20 (t, J )
flow. The reaction was monitored by thin-layer chromatography.
After the reactant disappeared, solvent was removed under reduced
pressure. Flash chromatography on silica gel eluting with hexane
and ethyl acetate (v/v, 10:1) gave the product.
1
.0 Hz, 2 H), 7.27 (d, J ) 7.8 Hz, 2 H), 7.34 (d, J ) 8.2 Hz, 2 H),
13
.69 (d, J ) 8.2 Hz, 1 H); C NMR (CDCl
3
, 75 MHz) δ 20.6,
0.9, 21.2, 21.6, 25.1, 28.6, 29.2, 32.7, 47.0, 118.7, 120.5, 126.4,
27.1, 128.6, 129.9, 130.6, 134.9, 140.4, 143.7; exact mass for
C H N S O (EI) calcd 379.1606, found 379.1601; IR (cm ) 2948
23 25 1 1 2
-1
2
a′: H NMR (CDCl
3
, 300 MHz) δ 0.60 (t, J ) 5.0 Hz, 1 H),
0
4
3
7
6
2
2
1
1
6
.70 (m, 1 H), 0.90-1.10 (m, 3 H), 1.46 (m, 1 H), 1.66 (dd, J )
.8 Hz, 8.9 Hz, 1 H), 2.13 (s, 3 H), 2.43 (s, 3 H), 2.72 (m, 2 H),
.09 (dd, J ) 3.2 Hz, 11.2 Hz, 1 H), 3.93 (m, 2 H), 4.39 (dd, J )
.4 Hz, 16.0 Hz, 1 H), 5.83 (m, 2 H), 6.68 (m, 2 H), 6.80 (m, 2 H),
.90 (m, 2 H), 7.28 (m, 2 H), 7.36 (m, 7 H), 7.80 (d, J ) 8.0 Hz,
(w), 2822 (w), 1620 (s), 1515 (s).
1
4f: H NMR (CDCl , 300 MHz) δ 1.03 (s, 3 H), 1.08 (s, 3 H),
3
1.33 (d, J ) 4.7 Hz, 1 H), 2.16 (m, 4 H), 2.45 (s, 3 H), 2.94 (d, J
) 11.5 Hz, 1 H), 3.93 (d, J ) 11.5 Hz, 1 H), 5.16 (d, J ) 7.9 Hz,
1 H), 6.28 (d, J ) 7.9 Hz, 1 H), 7.00 (d, J ) 7.8 Hz, 2 H), 7.15
H); 13C NMR (CDCl
, 75 MHz) δ 18.6, 20.0, 21.6, 21.8, 23.2,
13
3
(m, 2 H), 7.35 (m, 3 H), 7.69 (d, J ) 7.8 Hz, 1 H); C NMR
3.5, 25.6, 26.6, 36.9, 41.1, 46.0, 53.7, 118.8, 124.3, 124.9, 126.5,
27.0, 127.3, 127.7, 127.9, 128.7, 129.3, 130.1, 134.1, 135.8, 141.5,
42.8, 142.9, 144.1; exact mass for C38
52.2429, found 652.2424; CCDC no. 603263; IR (cm ) 2956
w), 2863 (w), 2121 (w), 1965 (w), 1915 (w), 1737 (br), 1658 (s),
(CDCl , 75 MHz) δ 18.4, 21.6, 27.6, 29.5, 29.8, 32.7, 34.0, 46.0,
3
119.0, 119.2, 122.2, 123.5, 126.1, 127.1, 127.5, 127.8, 129.9, 134.9,
H
40
N
2
S
2
O
4
(EI) calcd
140.5, 143.7; exact mass for C H S O N (EI) calcd 393.1762,
25
27
1
2
1
-
1
-1
obsd 393.1764; IR (cm ) 3080 (w), 3057 (w), 3022 (w), 2997
(w), 2908 (m), 2862 (m), 1948 (w), 1925 (w), 1899 (w), 1813 (w),
1699 (w), 1628 (s), 1595 (s).
(
1597 (s).
3g: IR (cm- ) 1754; H NMR (CDCl , 300 MHz) δ 1.60 (s, 3
1
1
N-Allyl-N-(3-cyclopropylprop-2-ynyl)-4-methylbenzenesulfon-
3
1
amide (1b): H NMR (CDCl
3
, 300 MHz) δ 0.28 (m, 1 H), 0.59
H), 1.61 (s, 3 H), 2.40 (m, 2 H), 2.62 (m, 2 H), 2.87 (m, 2 H), 3.04
(s, 2 H), 3.76 (s, 6 H), 5.61 (s, 1 H), 7.28 (m, 3 H), 7.38 (m, 2 H);
(
4
m, 1 H), 0.91 (m, 1 H), 2.41 (s, 3 H), 3.77 (d, J ) 6.3 Hz, 1 H),
13
.00 (d, J ) 1.7 Hz, 1 H), 5.22 (m, 2 H), 5.70 (m, 1 H), 7.28 (d,
3
C NMR (CDCl , 75 MHz) δ 18.3, 18.6, 34.1, 36.9, 39.4, 52.9,
1
3
J ) 8.1 Hz, 2 H), 7.69 (d, J ) 8.2 Hz, 2H); C NMR (CDCl
3
, 75
57.0, 84.0, 85.0, 122.8, 122.9, 123.4, 125.2, 128.1, 128.4, 129.8,
131.8, 171.1; exact mass for C H O (EI) calcd 366.1831, found
MHz) δ -0.9, 7.9, 21.6, 36.4, 49.0, 67.6, 89.4, 119.7, 127.8, 129.4,
23
26
4
1
2
32.2, 136.2, 143.4; exact mass for C16
H
19
N
1
S
1
O
2
(EI) calcd
366.4501.
89.1137, found 289.1139; IR (cm-1) 2944 (w), 2848 (w), 2224
4
-Methyl-N-(prop-2-ynyl)-N-(3-p-tolylprop-2-ynyl)benzene-
(m), 1721 (s), 1635 (s), 1590 (w).
1
sulfonamide (1h): H NMR (CDCl
2.33 (s, 3 H), 2.37 (s, 3 H), 4.20 (s, 2 H), 4.40 (s, 2 H), 7.06 (m,
3
, 300 MHz) δ 2.20 (s, 1 H),
1
6-Cyclopropyl-3-tosyl-3-azabicyclo[4.1.0]hept-4-ene (2b): H
1
3
NMR (CDCl
3
, 300 MHz) δ 0.02 (m, 2 H), 0.31 (m, 2 H), 0.40 (m,
4 H), 7.27 (d, J ) 7.1 Hz, 2 H), 7.75 (d, J ) 8.1 Hz, 1 H);
C
1
H), 0.54 (m, 1 H), 1.00 (m, 1 H), 2.44 (s, 3 H), 2.99 (dd, J ) 2.5
NMR (CDCl , 75 MHz) δ 21.43, 21.46, 36.5, 37.2, 73.9, 80.6, 86.0,
3
Hz, 11.5 Hz, 1 H), 3.87 (d, J ) 11.4 Hz, 1 H), 5.37 (d, J ) 8.1 Hz,
H), 6.35 (d, J ) 8.1 Hz, 1 H), 7.33 (d, J ) 8.4 Hz, 1 H), 7.67 (d,
100.0, 119.1, 127.9, 128.9, 129.6, 131.5, 135.4, 138.7, 143.8; exact
1
mass for C H N S O (EI) calcd 337.1136, found 337.1139; IR
2
0
19
1
1
2
1
3
-1
J ) 8.2 Hz, 1 H); C NMR (CDCl
7.1, 18.0, 21.6, 23.4, 40.9, 116.0, 120.4, 127.0, 129.7, 134.9, 143.7;
exact mass for C16 (EI) calcd 289.1137, found 289.1137;
IR (cm ) 2960 (w), 2912 (w), 2840 (m), 2288 (w), 1615 (s), 1580
w).
N-Allyl-N-(3-cyclohexenylprop-2-ynyl)-4-methylbenzenesulfon-
3
, 75 MHz) δ 2.1, 2.2, 15.1,
(cm ) 2966 (w), 2914 (w), 2239 (m), 2123 (w), 1655 (w), 1595
(s).
1
19 1 1 2
H N S O
N-((4,5-Dimethylcyclohexa-1,4-dienyl)methyl)-4-methyl-N-(3-
-
1
1
p-tolylprop-2-ynyl)benzenesulfonamide (3h): H NMR (CDCl
3
,
(
3
00 MHz) δ 1.63 (s, 3 H), 1.65 (s, 3 H), 2.32 (s, 6 H), 2.63 (s, 4
H), 3.78 (s, 2 H), 4.22 (s, 2 H), 5.71 (s, 1 H), 6.94 (d, J ) 7.5 Hz,
1
amide (1d): H NMR (CDCl
3
, 300 MHz) δ 1.53 (m, 4 H), 1.80
2 H), 7.03 (d, J ) 7.5 Hz, 1 H), 7.23 (d, J ) 7.9 Hz, 2 H), 7.77 (d,
J ) 8.0 Hz, 2 H); 13C NMR (CDCl , 75 MHz) δ 18.1, 18.4, 21.4,
(m, 2 H), 2.02 (m, 2 H), 2.41 (s, 3 H), 3.81 (d, J ) 6.4 Hz, 2 H),
3
4
2
2
1
.18 (s, 2 H), 5.26 (m, 2 H), 5.75 (m, 2 H), 7.29 (d, J ) 8.1 Hz,
H), 7.73 (d, J ) 8.3 Hz, 2 H); 13C NMR (CDCl
, 75 MHz) δ
1.5, 21.6, 22.3, 29.0, 36.8, 49.1, 78.8, 87.7, 119.86, 119.9, 127.9,
33.7, 33.8, 36.3, 52.3, 81.1, 85.7, 119.3, 122.4, 123.2, 125.1, 127.8,
128.8, 129.4, 129.5, 131.4, 136.2, 138.4, 143.3; exact mass for
3
-1
C H N S O (EI) calcd 419.1919, found 419.1924; IR (cm ) 2970
26
29
1
1
2
29.6, 132.2, 135.2, 136.2, 143.4; exact mass for C19
H
23
N
1
S
1
O
2
(w), 2918 (w), 2046 (m), 1606 (s), 1508 (s).
(
(
EI) calcd 329.1450, found 329.1449; IR (cm-1) 2912 (w), 2864
1
4
h: H NMR (CDCl
3
, 300 MHz) δ 1.05 (s, 3 H), 1.10 (s, 3 H),
w), 2208 (m), 1638 (w), 1587 (w).
1
.29 (d, J ) 4.6 Hz, 1 H), 2.17 (m, 4 H), 2.25 (s, 3 H), 2.45 (s, 3
1
6-Cyclohexenyl-3-tosyl-3-azabicyclo[4.1.0]hept-4-ene (2d): H
H), 2.93 (d, J ) 11.5 Hz, 1 H), 3.91 (d, J ) 11.5 Hz, 1 H), 5.12
(t, J ) 10.5 Hz, 1 H), 6.26 (d, J ) 7.9 Hz, 1 H), 6.88 (d, J ) 8.0
Hz, 2 H), 6.96 (d, J ) 7.8 Hz, 2 H), 7.34 (d, J ) 8.0 Hz, 1 H),
NMR (CDCl
3
, 300 MHz) δ 0.53 (m, 1 H), 0.98 (m, 1 H), 1.55 (m,
5
H), 1.87 (m, 2 H), 1.97 (m, 2 H), 2.44 (s, 3 H), 3.05 (dd, J ) 2.7
J. Org. Chem, Vol. 71, No. 25, 2006 9369

Lee et al.
-1
7
2
1
.69 (d, J ) 8.2 Hz, 1 H); 13C NMR (CDCl
3
, 75 MHz) δ 18.4,
1.0, 21.6, 27.3, 29.5, 29.8, 32.7, 33.9, 46.1, 118.9, 119.6, 122.1,
23.3, 127.1, 127.4, 128.5, 129.8, 135.1, 135.4, 137.4, 143.6; exact
433.2076; IR (cm ) 3039 (w), 2968 (w), 2908 (m), 2858 (m), 2851
(m), 2218 (w), 1597 (s).
1
4k: H NMR (CDCl , 300 MHz) δ 1.02 (s, 3 H), 1.07 (s, 3 H),
3
mass for C26
H
29
N
1
S O
1 2
(EI) calcd 419.1919, found 419.1920; IR
1.27 (m, 1 H), 2.14 (m, 4 H), 2.21 (s, 6 H), 2.45 (s, 3 H), 2.92 (d,
J ) 11.5 Hz, 1 H), 3.92 (d, J ) 11.6 Hz, 1 H), 5.16 (d, J ) 7.9
Hz, 1 H), 6.26 (d, J ) 7.2 Hz, 1 H), 6.61 (s, 2 H), 6.75 (s, 1 H),
-
1
(
(
cm ) 3080 (w), 3057 (w), 3022 (w), 2997 (w), 2908 (m), 2862
m), 1948 (w), 1925 (w), 1899 (w), 1813 (w), 1699 (w), 1628 (s),
1
3
1595 (s).
7.34 (d, J ) 7.9 Hz, 2 H), 7.69 (d, J ) 8.3 Hz, 2 H); C NMR
(CDCl , 75 MHz) δ 18.5, 18.54, 21.4, 21.8, 27.5, 30.0, 32.9, 34.2,
46.2, 119.1, 119.5, 122.3, 123.6, 125.3, 127.2, 127.9, 130.0, 135.0,
137.3, 140.5, 143.8; exact mass for C27 (EI) calcd
433.2075, found 433.2074; IR (cm ) 3026 (w), 2997 (w), 2966
(w), 1639 (s), 1599 (s).
N-(3-(4-Methoxyphenyl)prop-2-ynyl)-4-methyl-N-(prop-2-
3
1
ynyl)benzenesulfonamide (1i): H NMR (CDCl
3
, 300 MHz) δ 2.20
(
t, J ) 2.2 Hz, 1 H), 2.36 (s, 3 H), 3.79 (s, 3 H), 4.19 (d, J ) 2.2
31 1 1 2
H N S O
-
1
Hz, 1 H), 4.38 (s, 2 H), 6.77 (d, J ) 8.7 Hz, 2 H), 7.11 (d, J ) 8.7
Hz, 2 H), 7.27 (d, J ) 8.0 Hz, 2 H), 7.74 (d, J ) 8.2 Hz, 2H);
NMR (CDCl
13
C
1
3
, 75 MHz) δ 21.5, 36.5, 37.3, 55.3, 74.0, 76.6, 79.8,
3l: H NMR (CDCl , 300 MHz) δ 1.63 (s, 3 H), 1.67 (s, 3 H),
2.11 (s, 3 H), 2.66 (m, 4 H), 3.88 (s, 2 H), 4.41 (s, 2 H), 5.77 (s,
3
85.8, 113.8, 114.2, 127.9, 129.6, 133.1, 135.2, 143.9, 159.8; exact
mass for C20
H
19
N
1
S
1
O
3
(EI) calcd 353.1086, found 353.1083; IR
1 H), 7.12 (d, J ) 8.0 Hz, 2 H), 7.27 (d, J ) 7.9 Hz, 1 H), 7.34 (t,
-
1
13
(
cm ) 2970 (w), 2931 (w), 2241 (m), 2121 (m), 1606 (s).
J ) 7.6 Hz, 1 H), 7.47 (m, 2 H), 7.80 (m, 5 H); C NMR (CDCl ,
3
1
3i: H NMR (CDCl
3
, 300 MHz) δ 1.63 (s, 3 H), 1.65 (s, 3 H),
75 MHz) δ 18.2, 18.5, 21.2, 33.8, 33.9, 36.5, 52.5, 83.9, 86.8, 120.1,
122.5, 123.2, 125.0, 125.4, 125.9, 126.4, 126.7, 127.7, 128.3, 128.8,
2.31 (s, 3 H), 2.32 (s, 3 H), 2.63 (s, 4 H), 3.78 (s, 2 H), 4.22 (s, 2
H), 5.71 (s, 1 H), 6.92 (d, J ) 7.9 Hz, 2 H), 7.03 (d, J ) 7.8 Hz,
29 1 1 2
129.5, 130.6, 133.0, 133.1, 136.1, 143.5; exact mass for C29H N S O
(EI) calcd 455.1919, found 455.1915; IR (cm ) 2979 (m), 2910
(m), 2860 (m), 2816 (m), 1728 (s), 1655 (w), 1597 (s).
13
-1
2
H), 7.23 (d, J ) 8.0 Hz, 2 H), 7.77 (d, J ) 8.1 Hz, 2 H);
C
3
NMR (CDCl , 75 MHz) δ 18.2, 18.4, 21.4, 33.7, 33.8, 36.3, 52.3,
8
1
4
1.1, 85.8, 119.3, 122.4, 123.2, 125.1, 127.8, 128.8, 129.4, 129.5,
31.4, 138.4, 143.3; exact mass for C26 (EI) calc
35.1868, found 435.1873; IR (cm ) 2962 (w), 2924 (w), 2241
N-(But-2-ynyl)-N-((4,5-dimethylcyclohexa-1,4-dienyl)methyl)-
1
H
29
N S O
1 1 3
4-methylbenzenesulfonamide (3l): H NMR (CDCl , 300 MHz)
3
-
1
δ 1.49 (t, J ) 2.1 Hz, 3 H), 1.61 (s, 3 H), 1.63 (s, 3 H), 2.41 (s, 3
H), 2.58 (m, 4 H), 3.67 (s, 2 H), 3.94 (d, J ) 2.1 Hz, 2 H), 5.64
(
m), 1605 (m), 1592 (s).
1
13
4
i: H NMR (CDCl
3
, 300 MHz) δ 1.07 (s, 3 H), 1.12 (s, 3 H),
(s, 1 H), 7.28 (d, J ) 8.1 Hz, 2 H), 7.73 (d, J ) 8.1 Hz, 2 H);
C
1
1
.28 (m, 1 H) 2.15 (m, 4 H), 2.45 (s, 3 H), 2.93 (d, J ) 11.6 Hz,
NMR (CDCl
52.2, 71.8, 81.6, 122.5, 123.3, 125.0, 128.1, 129.3, 129.7, 136.4,
143.3; exact mass for C20 (EI) calcd 343.1606, found
3
, 75 MHz) δ 3.4, 18.3, 18.6, 21.7, 33.8, 33.9, 36.0,
H), 3.74 (s, 3 H), 3.91 (d, J ) 11.6 Hz, 1 H), 5.14 (d, J ) 7.9
Hz, 1 H), 6.25 (d, J ) 7.9 Hz, 1 H), 6.71 (d, J ) 8.7 Hz, 2 H),
25 1 1 2
H N S O
-1
6
8
2
1
.93 (d, J ) 8.7 Hz, 1 H), 7.34 (d, J ) 8.0 Hz, 1 H), 7.69 (d, J )
343.1610; IR (cm ) 3053 (w), 3026 (w), 2979 (m), 2918 (s), 2858
(s), 2817 (s), 2299 (m), 2252 (m), 1628 (s), 1597 (s).
4l: H NMR (CDCl , 300 MHz) δ 0.81 (s, 3 H), 0.89 (d, J )
7.2 Hz, 1 H), 1.54 (s, 3 H), 1.55 (s, 3 H), 1.88 (m, 1 H), 1.96 (m,
.2 Hz, 1 H); 13C NMR (CDCl
3
, 75 MHz) δ 18.39, 18.43, 21.6,
1
6.9, 29.5, 29.8, 32.7, 34.0, 46.1, 55.2, 113.3, 118.9, 119.6, 122.1,
23.3, 127.1, 128.5, 129.8, 132.9, 135.0, 143.7, 157.9; exact mass
3
for C26
H
29
N
1
S
1
O
3
(EI) calcd 435.1868, found 435.1873; CCDC no.
2 H), 2.12 (m, 1 H), 2.42 (s, 3 H), 2.76 (d, J ) 11.3 Hz, 1 H), 3.80
-
1
6
03264; IR (cm ) 2992 (w), 2908 (w), 1607 (m), 1513 (s).
(d, J ) 11.3 Hz, 1 H), 5.17 (d, J ) 7.9 Hz, 1 H), 6.22 (d, J ) 7.9
1
13
3j: H NMR (CDCl
3
, 300 MHz) δ 1.63 (s, 3 H), 1.66 (s, 3 H),
Hz, 1 H), 7.31 (d, J ) 7.9 Hz, 2 H), 7.64 (d, J ) 7.8 Hz, 2 H);
C
2
1
.22 (s, 3 H), 2.63 (m, 4 H), 3.84 (s, 2 H), 4.28 (s, 2 H), 5.78 (s,
H), 7.14 (m, 5 H), 7.50 (d, J ) 7.7 Hz, 1 H), 7.76 (d, J ) 8.2
NMR (CDCl
29.7, 31.1, 46.1, 119.3, 120.0, 122.6, 124.2, 127.2, 129.9, 135.1,
143.7; exact mass for C20 (EI) calcd 343.1606, found
3
, 75 MHz) δ 12.1, 18.7, 18.9, 19.3, 21.7, 25.4, 27.8,
13
Hz, 2 H); C NMR (CDCl
3
, 75 MHz) δ 18.1, 18.4, 21.3, 33.7,
25 1 1 2
H N S O
-1
33.8, 36.2, 52.3, 84.1, 86.7, 122.4, 123.2, 124.0, 125.1, 125.5, 126.7,
343.1610; IR (cm ) 2991 (w), 2958 (w), 2920 (w), 2858 (w), 1651
(s), 1595 (s), 1493 (s).
3n: H NMR (CDCl , 300 MHz) δ 0.87 (t, J ) 7.5 Hz, 3 H),
1
27.8, 129.3, 129.4, 132.2, 133.4, 136.0, 143.4; exact mass for
-
1
1
C
25
26
H N
1
S
1
O
2
Br
1
(EI) calcd 483.0868, found 483.0864; IR (cm
)
3
2910 (w), 2868 (w), 2843 (w), 2812 (w), 1969 (w), 1927 (m), 1664
1.63 (s, 3 H), 1.65 (s, 3 H), 1.87 (tq, J ) 2.2 Hz, 7.4 Hz 1 H,),
2.42 (s, 3 H), 2.58 (m, 4 H), 3.70 (s, 2 H), 3.98 (d, J ) 2.2 Hz, 2
H), 5.66 (s, 1 H), 7.29 (d, J ) 8.2 Hz, 2 H), 7.74 (d, J ) 8.2 Hz,
(
m), 1628 (m), 1597 (s).
1
4
3
j: H NMR (CDCl , 300 MHz) δ 0.87 (m, 1 H), 1.06 (s, 3 H),
1
1
.20 (s, 3 H), 2.32 (m, 4 H), 2.45 (s, 3 H), 3.29 (d, J ) 11.7 Hz,
H), 3.90 (d, J ) 11.7 Hz, 1 H), 5.08 (d, J ) 7.9 Hz, 1 H), 6.39
2 H); 13C NMR (CDCl
3
, 75 MHz) δ 12.3, 13.7, 18.3, 18.6, 21.7,
33.8, 33.9, 36.0, 52.1, 71.8, 87.6, 122.5, 123.3, 125.0, 128.0, 129.4,
129.7, 136.5, 143.3; exact mass for C21 (EI) calcd
(
7
d, J ) 7.9 Hz, 1 H), 7.00 (m, 2 H), 7.12 (m, 2 H), 7.34 (m, 1 H),
27 1 1 2
H N S O
13
-1
.41 (d, J ) 7.9 Hz, 1 H), 7.70 (d, J ) 7.9 Hz, 2 H); C NMR
, 75 MHz) δ 18.4, 18.43, 21.6, 29.9, 30.1, 32.7, 35.0, 44.8,
357.1763, found 357.1756; IR (cm ) 2987 (w), 2914 (w), 2289
(s), 2227 (s), 1932 (s), 1816 (s), 1741 (s), 1702 (s), 1664 (s).
(CDCl
3
1
1
17.5, 117.6, 120.1, 122.2, 124.2, 124.5, 126.6, 127.1, 127.14,
4n: H NMR (CDCl , 300 MHz) δ 0.91 (t, J ) 7.5 Hz, 3 H),
3
127.9, 129.8, 129.82, 133.0, 133.2, 135.2, 140.8, 143.6; exact mass
1.16 (m, 1 H), 1.55 (s, 3 H), 1.57 (s, 3 H), 2.00 (q, J ) 7.4 Hz, 2
H), 2.43 (s, 3 H), 2.82 (d, J ) 11.4 Hz, 1 H), 3.80 (d, J ) 11.4 Hz,
-1
26 1 1 2 1
for C25H N S O Br (EI) calc 483.0868, found 483.0864; IR (cm )
2989 (w), 2912 (w), 1637 (s), 1599 (s).
1 H), 5.30 (d, J ) 8.1 Hz, 1 H), 6.32 (d, J ) 8.0 Hz, 1 H), 7.32 (d,
1
13
1k: H NMR (CDCl
3
, 300 MHz) δ 2.20 (t, J ) 2.5 Hz, 1 H),
J ) 8.1 Hz, 2 H), 7.66 (d, J ) 8.1 Hz, 2 H); C NMR (CDCl
3
, 75
2
.24 (s, 6 H), 2.36 (s, 3 H), 4.18 (d, J ) 2.4 Hz, 1 H), 4.39 (s, 2
MHz) δ 11.6, 18.5, 18.7, 19.4, 21.5, 24.3, 25.9, 27.8, 30.1, 31.1,
H), 6.79 (s, 2 H), 6.91 (s, 1 H), 7.27 (d, J ) 7.8 Hz, 2 H), 7.75 (d,
46.4, 117.3, 120.0, 122.7, 124.2, 127.0, 129.7, 135.2, 143.5; exact
13
J ) 8.3 Hz, 1 H); C NMR (CDCl
3
, 75 MHz) δ 21.1, 21.6, 36.6,
7.3, 74.1, 76.7, 80.6, 86.4, 121.9, 128.1, 129.4, 129.7, 130.5, 135.5,
37.8, 143.9; exact mass for C21 (EI) calcd 351.1293,
27 1 1 2
mass for C21H N S O (EI) calcd 357.1763, found 357.1756; IR
-
1
3
1
(cm ) 2970 (w), 2920 (w), 1928 (w), 1816 (w), 1647 (s), 1598
H
21
N S
1 1
O
2
(s).
-
1
found 351.1295; IR (cm ) 3033 (w), 2218 (m), 2133 (m), 1927
N-(3-Cyclopropylprop-2-ynyl)-4-methyl-N-(prop-2-ynyl)ben-
1
(m).
zenesulfonamide (1o): H NMR (CDCl , 300 MHz) δ 0.37 (m, 2
3
1
3k: H NMR (CDCl
3
, 300 MHz) δ 1.63 (s, 3 H), 1.66 (s, 3 H),
H), 0.61 (m, 2 H), 1.02 (m, 1 H), 2.12 (t, J ) 2.1 Hz, 1 H), 2.38
(s, 3 H), 4.02 (m, 4 H), 7.27 (d, J ) 7.9 Hz, 2 H), 7.63 (d, J ) 8.0
2
2
.25 (s, 6 H), 2.35 (s, 3 H), 2.64 (m, 4 H), 3.77 (s, 2 H), 4.22 (s,
H), 5.70 (s, 1 H), 6.64 (s, 2 H), 6.91 (s, 1 H), 7.27 (d, J ) 8.0
Hz, 2 H); 13C NMR (CDCl
36.8, 67.2, 73.8, 76.6, 89.7, 127.9, 129.5, 135.3, 143.9; exact mass
for C16H N S O (EI) calcd 287.0980, found 287.0985; IR (cm )
17 1 1 2
, 75 MHz) δ -0.7, 8.0, 21.6, 36.2,
3
13
Hz, 1 H), 7.78 (d, J ) 8.3 Hz, 2 H); C NMR (CDCl
δ 18.4, 18.6, 21.3, 21.7, 33.8, 33.9, 36.4, 52.4, 81.0, 86.1, 122.1,
3
, 75 MHz)
-1
1
1
22.6, 123.4, 125.4, 128.0, 129.3, 129.5, 129.6, 130.4, 136.2, 137.8,
43.4; exact mass for C27 (EI) calcd 433.2075, found
3010 (w), 2970 (w), 2921 (w), 2848 (w), 2368 (m), 2247 (m), 1635
(s), 1590 (w).
31 1 1 2
H N S O
9370 J. Org. Chem., Vol. 71, No. 25, 2006

Au(I)-Catalyzed Cyclization of Enynes Bearing an Olefinic Cycle
1
1
3
o: H NMR (CDCl
3
, 300 MHz) δ 0.28 (m, 2 H), 0.57 (m, 2
7: H NMR (CDCl
Hz, 2 H), 4.44 (s, 2 H), 6.58 (t, J ) 4.1 Hz, 1 H), 7.14-7.60 (m,
13 H); 13C NMR (CDCl
, 75 MHz) δ 21.5, 44.1, 45.4, 119.9, 120.1,
122.0, 125.4, 127.5, 127.8, 128.2, 128.2, 128.5, 129.0, 129.7, 133.8,
3
, 300 MHz) δ 2.28 (s, 3 H), 4.15 (d, J ) 4.1
H), 1.64 (s, 3 H), 1.66 (s, 3 H), 2.43 (s, 3 H), 2.55-2.60 (m, 4 H),
.68 (s, 2 H), 3.95 (s, 2 H), 5.64 (s, 1 H), 7.27 (d, J ) 7.9 Hz, 2
H), 7.63 (d, J ) 8.0 Hz, 2 H); C NMR (CDCl
.0, 18.4, 18.6, 21.7, 33.8, 36.0, 52.1, 67.8, 89.4, 122.5, 123.4,
25.0, 128.0, 129.5, 129.7, 136.5, 143.3; exact mass for C22
EI) calcd 369.1763, found 369.1760; IR (cm-1) 2995 (w), 2916
w), 2852 (w), 2809 (w), 2310 (w), 2251 (w), 1932 (w), 1836 (w),
3
3
13
3
, 75 MHz) δ -0.7,
8
1
(
(
1
21 1 1 2
133.9, 134.4, 137.5, 139.0, 142.1, 143.8; exact mass for C25H N S O
(EI) calcd 399.1293, found 399.1297
t: H NMR (CDCl
.35 (s, 3 H), 2.58 (dt, J ) 2.7 Hz, 7.3 Hz, 2 H), 3.44 (t, J ) 7.3
Hz, 2 H), 4.42 (s, 2 H), 7.08 (m, 2 H), 7.27 (m, 5 H), 7.76 (d, J )
8.0 Hz, 2 H); C NMR (CDCl
70.6, 81.0, 82.0, 85.9, 122.2, 127.9, 128.4, 128.8, 131.7, 136.0,
143.7; exact mass for C20 (EI) calcd 337.1136, found
337.1141; IR (cm ) 2976 (w), 3269 (w), 2991 (w), 2947 (w), 2237
(w), 1967 (m), 1924 (w), 1660 (m), 1595 (s).
H
27
N
1
S
1
O
2
1
1
3
, 300 MHz) δ 2.03 (t, J ) 2.7 Hz, 1 H),
2
670 (s), 1597 (s).
1
13
4
o: H NMR (CDCl
3
, 300 MHz) δ 0.33 (m, 4 H), 0.94 (m, 1
3
, 75 MHz) δ 19.3, 21.6, 38.4, 45.7,
H), 0.97(d, J ) 5.5 Hz, 1 H), 1.55 (s, 3 H), 1.58 (s, 3 H), 2.00 (m,
H), 2.42 (s, 3 H), 2.97 (d, J ) 11.4 Hz, 1 H), 3.81 (d, J ) 11.4
Hz, 1 H), 4.79 (d, J ) 8.3 Hz, 1 H), 6.11 (d, J ) 8.3 Hz, 1 H),
4
19 1 1 2
H N S O
-1
7
(
3
1
3
.30 (d, J ) 8.0 Hz, 2 H), 7.64 (d, J ) 8.0 Hz, 2 H); 13C NMR
CDCl , 75 MHz) δ -0.1, 1.3, 6.1, 19.0, 21.8, 23.4, 26.7, 27.9,
0.8, 31.3, 46.1, 112.5, 120.4, 122.9, 124.5, 127.2, 129.9, 135.1,
43.7; exact mass for C22 (EI) calcd 369.1763, found
69.1761; IR (cm ) 2991 (w), 2958 (w), 2920 (w), 2858 (w), 1651
1
3
3
3t: H NMR (CDCl , 300 MHz) δ 1.61 (s, 6 H), 2.30 (m, 5 H),
2.56 (m, 4 H), 3.36 (m, 2 H), 4.36 (s, 2 H), 5.49 (s, 1 H), 7.02 (m,
H
27
N S O
1 1 2
2 H), 7.21 (m, 5 H), 7.76 (d, J ) 8.0 Hz, 2 H); 13C NMR (CDCl3,
-1
75 MHz) δ 18.4, 18.7, 21.6, 34.0, 35.4, 35.8, 37.2, 44.9, 81.9, 85.9,
(
s), 1595 (s), 1493 (s).
121.6, 122.3, 123.0, 123.1, 127.9, 128.3, 128.6, 129.7, 131.7, 132.0,
5
: 1H NMR (CDCl
3
, 300 MHz) δ 0.34 (m, 2 H), 0.64 (m, 2 H),
29 1 1 2
135.9, 143.6; exact mass for C26H N S O (EI) calcd 419.1919,
found 419.1927; IR (cm ) 2922 (w), 2857 (w), 2807 (w), 1920
(w), 1735 (w), 1598 (m).
-
1
0
2
.88 (m, 1 H), 1.18 (m, 1 H), 1.51 (s, 3 H), 1.62 (s 3 H), 1.84 (m,
H), 2.04 (m, 1 H), 2.31 (m, 1 H), 2.44 (s, 3 H), 2.85 (d, J ) 9.8
Hz, 1 H), 3.35 (d, J ) 9.8 Hz, 1 H), 3.71 (m, 2 H), 7.33 (d, J )
4-Methyl-N-(4-phenylbut-3-ynyl)-N-(prop-2-ynyl)benzene-
1
8
.0 Hz, 2 H), 7.72 (d, J ) 8.0 Hz, 2 H); 13C NMR (CDCl
MHz) δ -0.1, 1.3, 6.1, 19.0, 21.8, 23.4, 26.7, 27.9, 30.8, 31.3,
6.1, 112.5, 120.4, 122.9, 124.5, 127.2, 129.9, 135.1, 143.7; exact
mass for C22 (EI) calcd 369.1763, found 369.1765; IR
3
, 75
sulfonamide (1u): H NMR (CDCl , 300 MHz) δ 2.02 (t, J ) 2.2
3
Hz, 1 H), 2.41 (s, 3 H), 2.75 (t, J ) 7.2 Hz, 2 H), 3.46 (t, J ) 7.2
Hz, 2 H), 4.25 (d, J ) 2.2 Hz, 2 H), 7.27 (m, 5 H), 7.37 (m, 2 H),
4
27 1 1 2
H N S O
7.76 (d, J ) 8.0 Hz, 2 H); 13C NMR (CDCl , 75 MHz) δ 20.0,
3
-
1
(
(
cm ) 2993 (w), 2960 (w), 2920 (w), 2858 (w), 1639 (s), 1584
s), 1467 (s).
N-(3-Cyclohexenylprop-2-ynyl)-4-methyl-N-(prop-2-ynyl)ben-
zenesulfonamide (1p): H NMR (CDCl
H), 1.88 (m, 2 H), 2.00 (m, 2 H), 2.15 (t, J ) 2.1 Hz, 1 H), 2.42
s, 3 H), 4.31 (d, J ) 2.1 Hz, 2 H), 4.28 (s, 2 H), 5.88 (s, 1 H),
21.6, 37.4, 45.6, 74.0, 76.6, 82.4, 86.3, 123.2, 127.7, 128.0, 129.6,
131.6, 135.9, 143.7; exact mass for C H N S O (EI) calcd
20
19
1
1
2
-
1
337.1136, found 337.1143; IR (cm ) 2976 (w), 3269 (w), 2991
(w), 2947 (w), 2237 (w), 1967 (m), 1924 (w), 1660 (m), 1595 (s).
N-((4,5-Dimethylcyclohexa-1,4-dienyl)methyl)-4-methyl-N-(4-
phenylbut-3-ynyl)benzenesulfonamide (3u): H NMR (CDCl ,
300 MHz) δ 1.58 (s, 3 H), 1.60 (s, 3 H), 2.41 (s, 3 H), 2.46 (m, 2
H), 2.62 (m, 4 H), 3.33 (m, 2 H), 3.76 (s, 2 H), 5.62 (s, 2 H), 7.27
1
3
, 300 MHz) δ 1.54 (m, 4
1
(
7
(
7
3
13
.29 (d, J ) 7.9 Hz, 2 H), 7.72 (d, J ) 8.0 Hz, 2 H); C NMR
, 75 MHz) δ 21.4, 21.6, 22.1, 25.5, 28.9, 36.2, 37.1, 73.8,
6.5, 78.3, 87.7, 119.8, 127.9, 129.5, 135.3, 135.6, 143.8; exact
(EI) calcd 327.1293, found 327.1293; IR
CDCl
3
1
3
(m, 5 H), 7.34 (m, 2 H), 7.72 (d, J ) 8.0 Hz, 2 H); C NMR
mass for C21
H
23
N
1
S O
1 2
(CDCl , 75 MHz) δ 18.3, 18.5, 20.1, 21.6, 33.9, 46.6, 54.9, 82.3,
3
-
1
(
(
cm ) 2928 (w), 2880 (w), 2352 (m), 2176 (m), 1590 (w), 1484
86.9, 122.6, 123.0, 123.6, 124.6, 127.3, 128.0, 128.4, 129.8, 130.8,
w).
3
131.7, 143.4; exact mass for C H N S O (EI) calcd 419.1919,
found 419.1927; IR (cm ) 2983 (w), 2947 (w), 2237 (w), 1967
(m), 1924 (w), 1660 (m), 1595 (s).
26
29
1
1
2
1
-1
p: H NMR (CDCl
3
, 300 MHz) δ 1.53 (m, 4 H), 1.63 (s, 3 H),
1
4
(
7
1
.64 (s, 3 H), 1.76 (m, 2 H), 1.98 (m, 2 H), 2.43 (s, 3 H), 2.60 (m,
H), 3.71 (s, 2 H), 4.20 (s, 2 H), 5.66 (s, 1 H), 5.73 (m, 1 H), 7.30
1
1v: H NMR (CDCl , 300 MHz) δ 1.53 (s, 3 H), 2.32 (s, 3 H),
3
d, J ) 7.9 Hz, 2 H), 7.74 (d, J ) 8.0 Hz, 2 H); 13C NMR (CDCl
3
,
2.36 (s, 3 H), 3.36 (s, 2 H), 3.76-3.83 (m, 4 H), 3.87 (s, 2 H),
5 MHz) δ 3.4, 18.3, 18.6, 21.7, 33.8, 33.9, 36.0, 52.2, 71.8, 81.6,
5.10 (m, 2 H), 5.45 (m, 1 H), 6.10 (m, 2 H), 7.22 (m, 4 H), 7.62
(m, 2 H); 13C NMR (CDCl , 75 MHz) δ 3.5, 21.64, 21.68, 22.1,
22.5, 123.3, 125.0, 128.1, 129.3, 129.7, 136.4, 143.3; exact mass
3
-1
for C25
H
N S O
31 1 1 2
(EI) calcd 409.2076, found 409.2073; IR (cm
)
36.1, 36.3, 36.7, 48.3, 71.3, 78.3, 78.6, 82.1, 118.7, 126.9, 127.8,
127.9, 129.5, 129.7, 134.6, 135.4, 136.7, 135.8, 135.9, 143.9; exact
mass for C H N S O (EI) calcd 510.1647, found 510.1648; IR
2
(
976 (w), 2920 (w), 2852 (w), 2817 (w), 2372 (w), 2345 (w), 2302
w), 2221 (w), 1637 (m), 1598 (m).
27
30
2
2
4
: 1H NMR (CDCl
(cm-1) 2976 (w), 2912 (w), 2304 (s), 1910 (br), 1795 (w), 1686
6
3
, 300 MHz) δ 0.89 (m, 1 H), 1.20 (m, 3 H),
1
2
2
.40 (m, 1 H), 1.50 (s, 3 H), 1.63 (s, 3 H), 1.76 (m, 3 H), 1.82 (m,
H), 1.99 (m, 2 H), 2.22 (m, 2 H), 2.41 (s, 3 H), 2.43 (m, 1 H),
.51 (m, 1 H), 3.81 (d, J ) 10.7 Hz, 1 H), 5.57 (d, J ) 8.1 Hz, 1
(m).
1
2v: H NMR (CDCl , 300 MHz) δ 1.56 (s, 3H), 2.41 (s, 3H),
3
2.45 (s, 3H), 2.58 (m, 2H), 2.75 (m, 1H), 3.02 (m, 1H), 3.55-4.02
H), 6.69(d, J ) 8.1 Hz, 1 H), 7.29 (d, J ) 7.9 Hz, 2 H), 7.67 (d,
(m, 7 H), 5.60 (m, 1 H), 5.80 (m, 1 H), 7.27 (m, 4 H), 7.67 (m, 4
13
13
J ) 8.0 Hz, 2 H); C NMR (CDCl
3
, 75 MHz) δ 19.4, 19.6, 21.7,
5.5, 25.7, 25.9, 31.0, 33.0, 36.6, 44.4, 49.7, 53.6, 102.3, 123.0,
24.2, 124.4, 127.1, 130.0, 132.3, 135.1, 135.7, 143.8; exact mass
H); C NMR (CDCl , 75 MHz) δ 3.44, 21.71, 28.13, 36.26, 39.57,
3
2
1
47.65, 48.85, 52.40, 71.62, 82.46, 122.69, 122.93, 127.07, 127.65,
128.03, 129.50, 129.89, 133.63, 134.70, 135.79, 143.70, 143.84;
exact mass for C H N S O (EI) calcd 510.1647, found 510.1648;
-1
31 1 1 2
for C25H N S O (EI) calcd 409.2076, found 409.2075; IR (cm )
991 (w), 2940 (w), 2920 (w), 2858 (w), 1655 (s), 1590 (s), 1458
27
30
2
2
4
-
1
2
CCDC no. 603266; IR (cm ) 2912 (s), 1910 (w), 1790 (w), 1596
(
s).
3
(s), 1488 (m).
4v: H NMR (CDCl
1
1
s: H NMR (CDCl
3
, 300 MHz) δ 1.63 (s, 3 H), 1.72 (s, 3 H),
3
, 500 MHz) δ 0.87 (s, 3 H), 1.84 (m, 1 H),
2
2
.19 (s, 3 H), 2.87 (m, 4 H), 3.84 (s, 2 H), 4.14 (s, 2 H), 6.72 (m,
1.97 (m, 1 H), 2.42 (m, 3 H), 2.43 (s, 3 H), 2.45 (s, 3 H), 2.98 (d,
J ) 11.5 Hz, 1 H), 3.37 (d, J ) 11.5 Hz, 1 H), 3.38 (d, J ) 11.5
Hz, 1 H), 3.94 (m, 1 H), 4.95 (d, J ) 8.1 Hz, 1 H), 5.50 (m, 1 H),
5.57 (m, 1 H), 6.50 (d, J ) 8.1 Hz, 1 H), 7.35 (m, 4 H), 7.64 (d,
13
H), 7.02-7.22 (m, 10 H), 7.64 (d, J ) 8.0 Hz, 2 H); C NMR
, 75 MHz) δ 18.0, 18.3, 21.5, 34.9, 35.6, 41.4, 48.1, 82.0,
5.4, 122.4, 122.6, 123.7, 124.8, 126.8, 127.8, 127.9, 128.2, 128.4,
(CDCl
3
8
1
(
(
29.5, 131.6, 136.3, 137.3, 141.3, 143.4; exact mass for C31
H
21
N
1
S
1
O
2
J ) 8.0 Hz, 2 H), 7.71 (d, J ) 8.0 Hz, 2 H); 13C NMR (CDCl
3
,
EI) calcd 481.2075, found 481.2074; IR (cm-1) 3080 (w), 3057
w), 3022 (w), 2997 (w), 2908 (m), 2862 (m), 1948 (w), 1925 (w),
125 MHz) δ 13.2. 21.86, 21.89, 22.1, 25.0, 27.6, 35.5, 36.7, 44.3,
49.5, 54.8, 112.2, 121.5, 124.8, 125.8, 127.4, 128.5, 129.9, 130.0,
1899 (w), 1813 (w), 1699 (w), 1628 (s), 1595 (s).
130.1, 130.2, 132.2, 134.4, 143.8, 144.4; exact mass for C27
30 2 2 4
H N S O
J. Org. Chem, Vol. 71, No. 25, 2006 9371

Lee et al.
(
(
EI) calcd 510.1647, found 510.1649; IR (cm-1) 2912 (s), 1638
m), 1590 (s), 1542 (w), 1488 (m).
Supporting Information Available: Detailed experimental
1
13
procedures, new characterization data, H and C NMR spectra of
all compounds, and crystallographic data (CIF) of 2a′, 2v, and 4i.
This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgment. This work was supported by the Korea
Research Foundation grant funded by the Korean Government
MOEHRD) (R02-2004-000-10005-0) and (KRF-2005-070-
C00072) and the SRC/ERC program of MOST/KOSEF (R11-
005-065).
(
2
JO061254R
9372 J. Org. Chem., Vol. 71, No. 25, 2006