GaCl3-catalyzed allenyne cycloisomerizations to allenenes

Article abstract of DOI:10.1021/jo061318y

Cycloisomerizations of allenynes to allenenes have been studied in the presence of catalytic amounts of [Au(PPh₃)]-SbF₆ in dichloromethane or GaCl₃ in toluene. Both catalytic systems are quite effective for terminal 1,6-al

Full text of DOI:10.1021/jo061318y

GaCl3-Catalyzed Allenyne Cycloisomerizations to
Allenenes
allenynes in the metal-catalyzed cycloisomerization is quite rare.
Recently, PtCl2-catalyzed cycloisomerizations of allenynes were
reported by Murakami’s and Malacria’s groups. We initially
5
Sang Ick Lee, So Hee Sim, Soo Min Kim, Kwang Kim, and
Young Keun Chung*
studied the use of gold-catalyzed cycloisomerization of al-
lenynes. However, the expected reaction did not proceed in
many cases. This limitation prompted us to investigate an
alternative, more reactive catalytic system. Herein, we describe
a cycloisomerization of allenynes upon treatment with a catalytic
Intelligent Textile System Research Center and Department of
Chemistry, College of Natural Sciences, Seoul National
UniVersity, Seoul 151-747, Korea
6
amount of GaCl3. Recently, the Chatani group reported that
ykchung@snu.ac.kr
GaCl3 is a highly active catalyst for the skeletal rearrangement
of 1,6-enynes and 1,7-enynes.
ReceiVed June 27, 2006
We initially screened various metal catalysts such as the
7
4
8
5
9
6
Grubbs catalyst, Au(L)Cl/AgX, FeCl3, PtCl2, InCl3, GaCl3,
1
0
and [Mn(CO)5]BF4 for the cycloisomerization of allenynes
(Table 1).
Unfortunately, when PtCl2, [Mn(CO)5]BF4, or FeCl3 was used
as a catalyst, the reactant was recovered. The use of Grubbs
catalyst led to polymerization of the reactant. When InCl3 was
used as a catalyst, 45% of the cycloisomerized product was
isolated with a recovery of 40% of the reactant. However, when
[Au(PPh3)]SbF6 and GaCl3 were used as a catalyst, the metath-
(
3) (a) Mukai, C.; Hirose, T.; Teramoto, S.; Kitagaki, S. Tetrahedron
2
005, 61, 10983. (b) Brummond, K. M.; Curran, D. P.; Mitasev, B.; Fischer,
Cycloisomerizations of allenynes to allenenes have been
S. J. Org. Chem. 2005, 70, 1745. (c) Cao, H.; Van Ornum, S. G.;
Deschamps, J.; Flippen-Anderson, J.; Laib, F.; Cook, J. M. J. Am. Chem.
Soc. 2005, 127, 933. (d) Alcaide, B.; Almendros, P. Eur. J. Org. Chem.
studied in the presence of catalytic amounts of [Au(PPh
3
)]-
SbF in dichloromethane or GaCl in toluene. Both catalytic
6
3
2
004, 3377. (e) Brummond, K. M.; Gao, D. Org. Lett. 2003, 5, 3491. (e)
Brummond, K. M.; Kerekes, A. D.; Wan, H. J. Org. Chem. 2002, 67, 5156.
f) Brummond, K. M.; Chen, H. F.; Fisher, K. D.; Kerekes, A. D.; Rickards,
systems are quite effective for terminal 1,6-allenynes.
However, they showed different reactivities toward allenynes
with di-substituents at the allenic terminal carbon. For the
(
B.; Sill, P. C.; Geib, S. J. Org. Lett. 2002, 4, 1931. (f) Mukai, C.; Nomura,
I.; Yamanishi, K.; Hanaoka, M. Org. Lett. 2002, 4, 1755. (g) Brummond,
K. M.; Lu, J. L.; Petersen, J. J. Am. Chem. Soc. 2000, 122, 4915. (h)
Brummond, K. M.; Lu, J. L. J. Am. Chem. Soc. 1999, 121, 5087. (i)
Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931. (j) Kent, J.
L.; Wan, H. H.; Brummond, K. M. Tetrahedron Lett. 1995, 36, 2407.
GaCl
sonable to high yields. However, for a Au(I)-catalyzed
reaction, a triene was obtained in a poor yield. Thus, GaCl
3
-catalyzed reactions, allenenes were obtained in rea-
3
serves as an effective catalyst for the cycloisomerization of
allenynes bearing a terminal alkyne to give cyclic allenenes
in reasonable to high yields.
(4) For reviews, see: (a) Diver, S. T.; Giessert, A. J. Chem. ReV. 2004,
104, 1317. (b) Lloyd-Jones, G. C. Org. Biomol. Chem. 2003, 1, 215. (c)
Aubert, C.; Buisine, O.; Malacria, M. Chem. ReV. 2002, 102, 813. (d) Trost,
B. M.; Toste, F. D.; Pinkerton, A. B. Chem. ReV. 2001, 101, 2067. (e)
Trost, B. M.; Krische, M. J. Synlett 1998, 1. For Au- and Pt-catalyzed enyne
cycloisomerizations, see: (f) Echavarren, A. M.; Nevado, C. Chem. Soc.
ReV. 2004, 33, 431. (g) Nieto-Oberhuber, C.; L o´ pez, S.; Echavarren, A. M.
J. Am. Chem. Soc. 2005, 127, 6179. (h) Mu n˜ oz, M. P.; Adrio, J.; Carretero,
J. C.; Echavarren, A. M. Organometallics 2005, 24, 1293. (i) 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. (j) M e´ ndez,
M.; Mu n˜ oz, M. P.; Nevado, C.; C a´ rdenas, D. J.; Echavarren, A. M. J. Am.
Chem. Soc. 2001, 123, 10511. (k) Oi, S.; Tsukamoto, I.; Miyano, S.; Inoue,
Y. Organometallics 2001, 20, 3704.
The transition-metal-catalyzed cyclization of enyne systems
1
has recently experienced tremendous developments. Allenynes
are quite attractive substrates due to their use in diverse synthetic
2
applications as well as in new reactions of unsaturated systems.
Recently, they have been widely used in intramolecular Pauson-
3
Khand reactions. However, allenynes still have been much less
involved in the transition-metal-catalyzed (or -mediated) cy-
clizations than their enyne analogues. Particlularly, transition-
(5) (a) Matsuda, T.; Kadowaki, S.; Goya, T.; Murakami, M. Synlett 2006,
575. (b) Cadran, N.; Cariou, K.; Herv e´ , G.; Aubert, C.; Fensterbank, L.;
Malacria, M.; Marco-Contelles, J. J. Am. Chem. Soc. 2004, 126, 3408.
(6) (a) Mamane, V.; Hannen, P.; F uˆ rstner, A. Chem. Eur. J. 2004, 10,
metal-catalyzed intramolecular cycloisomerizations of enynes
have recently been widely studied.4 However, the use of
4556. (b) Chatani, N.; Oshita, M.; Tobisu, M.; Ishii, Y.; Murai, S. J. Am.
Chem. Soc. 2003, 125, 7812. (c) Chatani, N.; Inoue, H.; Kotsuma, T.; Murai,
S. J. Am. Chem. Soc. 2002, 124, 10294. (d) F uˆ rstner, A.; Mamane, V. J.
Org. Chem. 2002, 67, 6264. (e) Inoue, H.; Chatani, N.; Murai, S. J. Org.
Chem. 2002, 67, 1414.
(7) (a) Peppers, B. P.; Diver, S. T. J. Am. Chem. Soc. 2004, 126, 9524.
(b) Schmidt, B. Angew. Chem., Int. Ed. 2003, 42, 4996. (c) Kitamura, T.;
Sato, Y.; Mori, M. AdV. Synth. Catal. 2002, 344, 678. (d) Mori, M.;
Sakakibara, N.; Kinoshita, A. J. Org. Chem. 1998, 63, 6082. (e) Kinoshita,
A.; Mori, M. Synlett 1994, 1020.
(8) Nieto-Oberhuber, C.; Mu n˜ oz, M. P.; L o´ pez, S.; Jim e´ nez-N u´ n˜ ez, E.;
Nevado, C.; Herrero-G o´ mez, E.; Raducan, M.; Echavarren, A. M. Chem.
Eur. J. 2006, 12, 1677.
(9) Miyanohana, Y.; Chatani, N. Org. Lett. 2006, 8, 2155.
(10) Recently, we found that [Mn(CO)5]BF4 was active in the cycloi-
somerization of some enyne substrates. Lee, S. I.; Baek, J. Y.; Chung, Y.
K. Manuscript in preparation.
(
1) For reviews, see: (a) Nakamura, I.; Yamamoto, Y. Chem. ReV. 2004,
1
04, 2127. (b) Fr u¨ hauf, H.-W. Chem. ReV. 1997, 97, 523. (c) Ojima, I.;
Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. ReV. 1996, 96, 635. (d)
Lautens, M.; Klute, W.; Tam, W. Chem. ReV. 1996, 96, 49.
(2) (a) Brummond, K. M.; You, L. F. Tetrahedron 2005, 61, 6180. (b)
Gupta, A. K.; Rhim, C. Y.; Oh, C. H. Tetrahedron Lett. 2005, 46, 2247.
c) Oh, C. H.; Park, D. I.; Jung, S. H.; Reddy, V. R.; Gupta, A. K.; Kim,
(
Y. M. Synlett 2005, 2092. (d) Kumareswaran, R.; Shin, S.; Gallou, I.;
RajanBabu, T. V. J. Org. Chem. 2004, 69, 7157. (e) Shibata, T.; Kadowaki,
S.; Takagi, K. Organometallics 2004, 23, 4116. (f) Mukai, C.; Inagaki, F.;
Yoshida, T.; Kitagaki, S. Tetrahedron Lett. 2004, 45, 4117. (g) Oh, C. H.;
Jung, S. H.; Park, D. I.; Choi, J. H. Tetrahedron Lett. 2004, 45, 2499. (h)
Oh, C. H.; Jung, S. H.; Rhim, C. Y. Tetrahedron Lett. 2001, 42, 8669. (i)
Urabe, H.; Takeda, T.; Hideura, D.; Sato. F. J. Am. Chem. Soc. 1997, 119,
1
1295.
10.1021/jo061318y CCC: $33.50 © 2006 American Chemical Society
7
120
J. Org. Chem. 2006, 71, 7120-7123
Published on Web 08/10/2006

TABLE 1. Allenyne Metathesis by Various Catalystsa
SCHEME 1
T
(°C)
t
yield
(%)b
entry
1
catalyst
solvent
CH2Cl2
(h)
5 mol % RuCl2(PCy3)2-
15-20
6
N/A
(
benzylidene)
2
3
4
5
6
7
5 mol % [Mn(CO)5]BF4
5 mol % FeCl3
5 mol % PtCl2
10 mol % InCl3
5 mol % [Au(PPh3)]SbF6
10 mol % GaCl3
DCE
60
80
80
80
15-20
15-20
24
24
24
24
NR
NR
NR
45(40)
toluene
toluene
toluene
CH2Cl2
toluene
0.5 75
81
2
allene (eq 1). Murakami et al.11 also observed the formation of
the same deuterated reaction product.
a
.2 g (0.691 mmol) of 1a in 5 mL of solvent was used. b Isolated yield.
0
c
d
DCE ) 1,2-dichloroethane. Yield in parentheses is reactant recovered.
esis product was isolated in 75% and 81% yield, respectively.
The obtained cycloisomerized product (1A) was the same type
as those obtained by the molybdenum alkylidene complex-
11
catalyzed ring-closing metathesis (RCM) of allenynes but quite
different from those obtained by PtCl2-catalyzed cycloisomer-
5
ization of allenynes. Encouraged by this result, several allenynes
were examined for GaCl3- and Au(I)-catalyzed metathesis
reactions (Table 2).
Next, when a crossover reaction using a mixture of 1h and
j was carried out in the presence of GaCl3, no crossover
1
products were obtained (eq 2). This observation was quite
different from the results observed in the molybdenum-catalyzed
reaction, where the crossover products were isolated.6
Terminal allenynes 1a-1c having sulfonamide or sulfone in
a tether were found to serve as good substrates for both GaCl3-
and Au(I)-catalyzed reactions (entries 1-5). This is in sharp
contrast to previously reported results on the Mo-catalyzed RCM
1
1
of allenynes, where no reaction occurred with allenynes
bearing the allenic terminus unsubstituted. Allenynes 1d-1g
having a substituent on the 3 position (entries 6-10) or having
a substituent on the 5 position (entries 11 and 12) were also
good substrates. However, allenynes with di-substituents at the
allenic terminal carbon showed a different behavior depending
upon the catalyst used. When GaCl3 was used as catalyst, an
allenyne (1h) (entry 13) afforded the product 2h in 60% yield
and allenynes 1i and 1j bearing a cyclic group on the allenic
terminal carbon (entries 14 and 15) were also good substrates
and led to the isolation of the products 2i and 2j in 53% and
A general mechanistic view has so far remained elusive.
However, our experimental observations suggest that the mech-
11
anism will be different from that proposed by Murakami but
6
8
3% yields, respectively. Thus, substantial structural variations
can be accommodated. Interestingly, when 1j was reacted with
Au(PPh3)]SbF6, a cycloisomerized product (3j) was isolated
will follow the general process depicted by Chatani (Scheme
1
2
2).
[
In conclusion, we have shown that the unprecedented GaCl3-
and Au(I)-catalyzed cycloisomerization of allenyne systems is
a highly versatile tool for obtaining products that cannot be
easily attained with other metals. Both catalytic systems are quite
effective for terminal 1,6-allenynes. However, they showed
different reactivities toward allenynes with di-substituents at the
allenic terminal carbon.
in low yield (38%). This transformation is similar to the PtCl2-
catalyzed cycloisomerization of allenynes reported by Muraka-
5
a
mi’s group. Thus, GaCl3 is a better catalyst for the cyclo-
isomerization of allenynes with di-substituents at the allenic
terminal carbon. Unfortunately, no reaction was observed for
allenynes having a substituent (1k and 1l) on the alkyne terminal
position (entries 17-19) and a 1,7-allenyne (1m) (entries 20
and 21) under the conditions described here.
Experimental Section
General Procedure for GaCl
lenyne. To a flame-dried 10 mL Schlenk containing 5 mL of toluene
were added GaCl (10 mol %, 14 mg) and allenyne (0.7 mmol)
3
-Catalyzed Metathesis of Al-
When allenene (1n) was reacted in the presence of GaCl3
catalyst (Scheme 1), an RCM product (3n) was obtained in 22%
yield with recovery of reactant in 76% yield. However, no
reaction was observed in the presence of Au(I) catalyst.
Treatment of 1,6-diene (1o) under the same reaction conditions
gave no reaction product. Thus, the GaCl3- and Au(I)-catalyzed
cycloisomerization were unique to allenyne substrates.
When allenyne 1a-d with the alkyne terminus deuterated was
used, the deuterium was labeled at the 1-position of the produced
3
sequentially. After the reactant disappeared, 1 mL of diisopropy-
lamine was added. After the reaction mixture was quenched, the
solvent was removed under reduced pressure. Flash column
chromatography gave the product.
3 6
General Procedure for AuCl(PPh )/AgSbF -Catalyzed Me-
tathesis of Allenyne. To a flame-dried 10 mL Schlenk containing
(
12) One of the referees suggested an alternative, path “b”, as a possible
(11) Murakami, M.; Kadowaki, S.; Matsuda, T. Org. Lett. 2005, 7, 3953.
reaction path.
J. Org. Chem, Vol. 71, No. 18, 2006 7121

TABLE 2. GaCl3- and [Au(PPh3)]SbF6-Catalyzed Metathesis of Allenynea
a
Condition A: 0.2 g (0.691 mmol) of allenyne and 10 mol % GaCl3 in 5 mL of toluene were used. Condition B: 0.2 g (0.691 mmol) of allenyne, 5 mol
%
AuCl(PPh3), and 7 mol % AgSbF6 in 5 mL of CH2Cl2 were used. b Isolated yield. c 20 mol % GaCl3 was used. d No reaction.
SCHEME 2
5
mL of CH
2
Cl
2
were added AuCl(PPh
3
) (5 mol %, 9 mg), AgSbF
6
N-(Buta-2,3-dienyl)-2,4,6-trimethyl-N-(prop-2-ynyl)benzene-
1
(7 mol %, 10 mg), and allenyne (0.7 mmol) sequentially. After the
sulfonamide (1b). H NMR (CDCl
Hz, 1 H), 2.29 (s, 3 H), 2.57 (s, 6 H), 3.85 (m, 2 H), 4.01(d, J )
2.2 Hz, 2 H), 4.77 (m, 2 H), 5.02 (m, 1 H), 6.92 (s, 2 H) ppm;
3
, 300 MHz) δ 2.19 (t, J ) 2.2
reactant disappeared, the solvent was removed under reduced
pressure. A flash column chromatography gave the product.
1
3
C
1
3-(Propa-1,2-dienyl)-1-tosyl-2,5-dihydro-1H-pyrrole (2a). H
NMR (CDCl , 75 MHz) δ 21.0, 22.8, 34.6, 44.7, 73.0, 76.3, 85.3,
3
NMR (CDCl
3
, 300 MHz) δ 2.35 (s, 3 H), 4.02 (m, 2 H), 4.09 (m,
H), 4.93 (m, 2 H), 5.42 (s, 1 H), 5.80 (t, J ) 6.6 Hz, 1 H), 7.25
d, J ) 8.0 Hz, 2 H), 7.65 (d, J ) 8.2 Hz, 2 H) ppm; 13C NMR
CDCl , 75 MHz) δ 21.7, 54.8, 55.7, 78.5, 87.8, 120.7, 127.6, 130.0,
33.0, 134.2, 143.7, 211.0 ppm. Exact mass for (C14
EI): (calcd) 261.0823, (found) 261.0825.
132.0, 132.3, 140.5, 142.8, 209.9 ppm. Exact mass for (C16
19 1 1 2
H N S O ,
2
(
(
EI): (calcd) 289.1137, (found) 289.1133.
1-(Mesitylsulfonyl)-3-(propa-1,2-dienyl)-2,5-dihydro-1H-pyr-
1
3
role (2b). H NMR (CDCl
H), 4.09 (m, 2 H), 4.13 (m, 2 H), 4.98 (m, 1 H), 5.59 (s, 1 H), 5.94
(m, 1 H), 6.96 (s, 3 H) ppm; 13C NMR (CDCl
, 75 MHz) δ 21.0,
3
, 300 MHz) δ 2.29 (s, 3 H), 2.63 (s, 6
1
15 1 1 2
H N S O ,
3
7
122 J. Org. Chem., Vol. 71, No. 18, 2006

2
2
2.9, 53.3, 54.3, 78.3, 87.8, 120.6, 131.9, 132.6, 132.7, 140.2, 142.5,
10.8. Exact mass for (C16 , EI): (calcd) 289.1137,
4-Methyl-N-(penta-3,4-dien-2-yl)-N-(prop-2-ynyl)benzene-
sulfonamide (1g). H NMR (CDCl , 300 MHz) δ 1.26 (d, J ) 6.2
3
1
H
19
N S O
1 1 2
(found) 289.1140.
Hz, 3 H), 2.17 (t, J ) 2.2 Hz, 1 H), 2.43 (s, 3 H), 3.96 (dd, J )
18.5, 2.2 Hz, 1 H), 4.15 (dd, J ) 18.5, 2.2 Hz, 1 H), 4.60 (m, 1 H),
4.82 (m, 2 H), 5.07 (q, J ) 6.2 Hz, 1 H), 7.29 (d, J ) 8.0 Hz, 2
1
1
3
c. H NMR (CDCl , 300 MHz) δ 1.94 (t, J ) 2.1 Hz, 1 H),
2
1
.93 (m, 2 H), 3.03 (d, J ) 2.1 Hz, 2 H), 4.63 (m, 2 H), 5.26 (m,
H), 7.40 (m, 4 H), 7.53 (d, J ) 7.4 Hz, 2 H), 7.95 (d, J ) 8.0
H), 7.80 (d, J ) 8.0 Hz, 2 H) ppm; 13C NMR (CDCl
3
, 75 MHz) δ
18.1, 21.7, 32.2, 52.0, 72.4, 78.1, 80.4, 91.8, 127.7, 129.7, 137.8,
13
3
Hz, 4 H) ppm; C NMR (CDCl , 75 MHz) δ 20.9, 29.2, 74.5,
7
5.7, 76.0, 83.0, 88.4, 128.7, 131.5, 135.0, 136.4, 210.5 ppm.
Exact mass for (C20 , EI): (calcd) 386.0647, (found)
86.0651.
143.6, 208.9 ppm. Exact mass for (C15
275.0980, (found) 275.0982.
17 1 1 2
H N S O , EI): (calcd)
18 1 1 2
H N S O
3
2-Methyl-4-(propa-1,2-dienyl)-1-tosyl-2,5-dihydro-1H-pyr-
1
1
2
c. H NMR (CDCl
3
, 300 MHz) δ 3.36-3.37 (m, 4 H), 4.97
3
role (2g). H NMR (CDCl , 300 MHz) δ 1.41 (d, J ) 6.2 Hz, 3
(m, 2 H), 5.11 (s, 1 H), 5.66 (m, 1 H), 7.54 (m, 4 H), 7.67 (m, 2
H), 2.42 (s, 3 H), 4.04 (m, 1 H), 4.16 (m, 1 H), 4.51 (m, 1 H), 4.99
13
H), 7.97 (m, 4 H) ppm; C NMR (CDCl
8.4, 89.3, 91.3, 122.8,129.0, 131.0, 134.9, 135.1, 137.0, 211.3 ppm.
Exact mass for (C20 , EI): (calcd) 386.0647, (found)
86.0651.
N-(But-3-yn-2-yl)-N-(buta-2,3-dienyl)-4-methylbenzenesulfona-
3
, 75 MHz) δ 39.1, 39.5,
(m, 2 H), 5.40 (m, 1 H), 5.88 (m, 1 H), 7.31 (d, J ) 8.0 Hz, 2 H),
7
7.72 (d, J ) 8.0 Hz, 2 H) ppm; 13C NMR (CDCl
3
, 75 MHz) δ
H N
18 1
S O
1 2
21.7, 23.0, 55.3, 64.0, 78.5, 87.7, 127.1, 127.6, 129.9, 131.4, 135.0,
3
143.6, 211.1 ppm. Exact mass for (C15
275.0980, (found) 275.0982.
17 1 1 2
H N S O , EI): (calcd)
1
mide (1d). H NMR (CDCl
H), 2.15 (d, J ) 2.2 Hz, 1 H), 2.43 (s, 3 H), 3.78 (m, 1 H), 3.97
m, 1 H), 4.78 (m, 2 H), 4.90 (dd, J ) 7.1, 2.2 Hz, 1 H), 5.23 (m,
H), 7.30 (d, J ) 8.0 Hz, 2 H), 7.74 (d, J ) 7.9 Hz, 2 H) ppm;
3
, 300 MHz) δ 1.49 (d, J ) 7.1 Hz, 3
N-(3-Cyclobutylideneallyl)-4-methyl-N-(prop-2-ynyl)benzene-
1
3
sulfonamide (1i). H NMR (CDCl , 300 MHz) δ 1.93 (m, 2 H),
(
2.01 (t, J ) 2.2 Hz, 1 H), 2.42 (s, 3 H), 2.81-2.87 (m, 4 H), 3.81
1
(s, 1 H), 3.83 (s, 1 H), 4.13 (d, J ) 2.2 Hz, 2 H), 4.98 (m, 1 H),
13
13
C NMR (CDCl
1.5, 89.3, 127.7, 129.7, 136.6, 143.6, 208.9 ppm. Exact mass for
, EI): (calcd) 275.0980, (found) 275.0982.
-Methyl-3-(propa-1,2-dienyl)-1-tosyl-2,5-dihydro-1H-pyr-
3
, 75 MHz) δ 21.8, 22.8, 44.0, 46.0, 73.4, 76.6,
7.28 (d, J ) 8.0 Hz, 2 H), 7.73 (d, J ) 8.0 Hz, 2 H) ppm;
C
8
NMR (CDCl
87.8, 103.0, 127.7, 129.5, 136.1, 143.5, 197.5 ppm. Exact mass
for (C17 , EI): (calcd) 301.1137, (found) 301.1134.
3-(2-Cyclobutylidenevinyl)-1-tosyl-2,5-dihydro-1H-pyrrole (2i).
3
, 75 MHz) δ 17.5, 21.6, 29.6, 35.6, 46.6, 73.4, 77.2,
15 16 1 1 2
(C H N S O
2
19 1 1 2
H N S O
1
role (2d). H NMR (CDCl , 300 MHz) δ 1.49 (d, J ) 6.6 Hz, 3
3
1
H), 2.43 (s, 3 H), 4.07-4.24 (m, 2 H), 4.54 (m, 1 H), 5.01 (m, 2
H), 5.45 (s, 1 H), 5.82 (t, J ) 6.6 Hz, 1 H), 7.31 (d, J ) 8.0 Hz,
H NMR (CDCl
3
, 300 MHz) δ 1.91 (m, 2 H), 2.33 (s, 3 H), 2.80
(m, 4 H), 4.03 (m, 2 H), 4.06 (m, 2 H), 5.38 (s, 1 H), 5.73 (m, 1
H), 7.72 (d, J ) 7.9 Hz, 2 H) ppm; 13C NMR (CDCl
H), 7.23 (d, J ) 8.0 Hz, 2 H), 7.64 (d, J ) 8.0 Hz, 2 H) ppm;
NMR (CDCl , 75 MHz) δ 17.4, 21.5, 29.9, 54.8, 55.5, 89.8, 103.9,
120.1, 127.2, 129.7, 134.3, 135.2, 143.4, 197.4 ppm. Exact mass
for (C17 , EI): (calcd) 301.1137, (found) 301.1136.
(E)-3-(Cyclohexenylmethylene)-4-methylene-1-tosylpyrroli-
13
C
2
3
, 75 MHz)
δ 21.6, 22.3, 54.5, 63.0, 78.5, 87.4, 120.3, 127.3, 129.8, 135.1,
1
2
3
16 1 1 2
43.5, 210.7 ppm. Exact mass for (C15H N S O , EI): (calcd)
75.0980, (found) 275.0982.
19 1 1 2
H N S O
N-(Buta-2,3-dienyl)-4-methyl-N-(pent-1-yn-3-yl)benzenesulfona-
1
1
mide (1e). H NMR (CDCl
H), 1.77 (qd, J ) 7.7, 3.3 Hz, 2 H), 2.13 (d, J ) 2.2 Hz, 1 H), 2.41
s, 3 H), 3.72 (m, 1 H), 3.91 (m, 1 H), 4.60 (td, J ) 7.6, 2.1 Hz,
H), 4.75 (m, 2 H), 5.26 (m, 1 H), 7.28 (d, J ) 7.9 Hz, 2 H), 7.73
d, J ) 7.9 Hz, 2 H) ppm; 13C NMR (CDCl
, 75 MHz) δ 10.7,
1.5, 29.0, 44.0, 52.2, 73.8, 76.2, 80.5, 88.9, 127.6, 129.4, 136.5,
3
, 300 MHz) δ 1.02 (t, J ) 7.7 Hz, 3
3
dine (3j). H NMR (CDCl , 300 MHz) δ 1.61 (m, 4 H), 1.93 (m,
2 H), 2.06 (m, 2 H), 2.45 (s, 3 H), 3.81 (m, 2 H), 3.85 (m, 2 H),
(
1
(
2
1
2
5.01 (s, 1 H), 5.02 (s, 1 H), 5.41-5.46 (m, 2 H), 7.30 (d, J ) 8.0
Hz, 2 H), 7.67 (d, J ) 8.0 Hz, 2 H) ppm; 13C NMR (CDCl
, 75
3
3
MHz) δ 21.7, 22.3, 23.1, 25.4, 28.9, 45.8, 49.8, 113.3, 120.7, 126.6,
128.1, 129.7, 133.9, 136.3, 136.5, 141.4, 143.7 ppm. Exact mass
43.4, 208.6 ppm. Exact mass for (C16
89.1137 (found) 289.1135.
19 1 1 2
H N S O , EI): (calcd)
for (C19
23 1 1 2
H N S O , EI): (calcd) 329.1449, (found) 329.1448.
N-(But-2-ynyl)-N-(buta-2,3-dienyl)-4-methylbenzenesulfon-
1
2
-Ethyl-3-(propa-1,2-dienyl)-1-tosyl-2,5-dihydro-1H-pyr-
3
amide (1k). H NMR (CDCl , 300 MHz) δ 1.49 (t, J ) 2.6 Hz, 3
1
role (2e). H NMR (CDCl
1
1
3
, 300 MHz) δ 0.82 (t, J ) 7.3 Hz, 3 H),
.78 (m, 1 H), 1.98 (m, 1 H), 2.40 (s, 3 H), 4.11 (m, 2 H), 4.62 (m,
H), 4.99 (m, 1 H), 5.48 (m, 1 H), 5.78 (m, 1 H), 7.27 (d, J ) 7.8
H), 2.35 (s, 3 H), 3.77 (m, 2 H), 4.00 (q, J ) 2.6 Hz, 2 H), 4.69
(m, 2 H), 4.97 (m, 1 H), 7.21 (d, J ) 8.0 Hz, 2 H), 7.65 (d, J ) 8.0
Hz, 2 H) ppm; 13C NMR (CDCl
, 75 MHz) δ ?3.4, 21.7, 36.6,
3
13
Hz, 2 H), 7.69 (d, J ) 7.8 Hz, 2 H) ppm; C NMR (CDCl
MHz) δ 7.1, 21.5, 26.4, 55.4, 67.5, 78.2, 82.2, 121.5, 127.2, 129.6,
35.1, 135.2, 143.3, 210.4 ppm. Exact mass for (C16
HRFAB): (calcd) 290.1215, (found) 290.1213.
N-(Buta-2,3-dienyl)-4-methyl-N-(1-phenylprop-2-ynyl)benze-
3
, 75
45.7, 71.8, 81.7, 85.8, 128.0, 129.5, 136.4, 143.5, 209.9 ppm. Exact
mass for (C15 , EI): (calcd) 275.0980, (found) 275.0981.
N-(But-3-ynyl)-N-(buta-2,3-dienyl)-4-methylbenzenesulfon-
17 1 1 2
H N S O
1
19 1 1 2
H N S O ,
1
amide (1m). H NMR (CDCl , 300 MHz) δ 1.87 (t, J ) 2.3 Hz,
3
1 H), 2.29 (s, 3 H), 2.36 (td, J ) 7.6 Hz, 2.3 Hz, 2 H), 3.22 (t, J
) 7.6 Hz, 2 H), 3.77 (m, 2 H), 4.60 (m, 2 H), 4.83 (m, 1 H), 7.17
1
nesulfonamide (1f). H NMR (CDCl , 300 MHz) δ 2.40 (d, J )
3
1
3
2
4
5
.2 Hz, 1 H), 2.44 (s, 3 H), 3.71-3.77 (m, 2 H), 4.42 (m, 1 H),
(d, J ) 8.0 Hz, 2 H), 7.57 (d, J ) 8.0 Hz, 2 H) ppm; C NMR
.51 (m, 1 H), 4.77 (m, 1 H), 6.11 (d, J ) 2.2 Hz, 1 H), 7.33 (m,
H), 7.60 (d, J ) 6.9 Hz, 2 H), 7.79 (d, J ) 8.0 Hz, 2 H) ppm;
3
(CDCl , 75 MHz) δ ?19.4, 21.7, 46.0, 47.5, 70.3, 76.7, 81.2, 86.1,
128.5, 129.9, 137.2, 143.6, 209.7 ppm. Exact mass for (C15
17 1 1 2
H N S O ,
13
3
C NMR (CDCl , 75 MHz) δ 21.8, 44.6, 53.3, 76.0, 78.4, 87.9,
EI): (calcd) 275.0980, (found) 275.0977.
128.0, 128.3, 128.6, 128.63, 128.7, 129.7, 136.0, 136.6, 143.8 ppm.
Acknowledgment. This work was supported by the Korean
Research Foundation Grant funded by the Korean Government
MOEHRD) (KRF-2005-070-C00072) and the SRC/ERC pro-
gram of MOST/KOSEF (R11-2005-065). S.I.L., S.H.S., S.M.K.,
and K.K. thank to the BK21 fellowship.
Exact mass for (C20
37.1137.
-Phenyl-3-(propa-1,2-dienyl)-1-tosyl-2,5-dihydro-1H-pyr-
19 1 1 2
H N S O , EI): (calcd) 337.1137, (found)
3
(
2
1
role (2f). H NMR (CDCl
H), 4.45 (m, 1 H), 4.61 (m, 1 H), 4.91 (m, 1 H), 5.59 (m, 1 H),
3
, 300 MHz) δ 2.42 (s, 3 H), 4.34 (m, 1
5
5
.76 (m, 1 H), 5.81 (m, 1 H), 7.17 (d, J ) 8.0 Hz, 2 H), 7.27 (m,
H), 7.43 (d, J ) 8.0 Hz, 2 H) ppm; 13C NMR (CDCl
Supporting Information Available: Characterization of new
compounds and H and C NMR data. This material is available
free of charge via the Internet at http://pubs.acs.org.
3
, 75 MHz)
1
13
δ ?21.6, 54.9, 55.0, 70.3, 78.7, 87.2, 121.2, 127.2, 127.9, 128.2,
28.5, 129.5, 136.2, 136.5, 140.0, 143.0, 211.4 ppm. Exact mass
for (C20 , EI): (calcd) 337.1137, (found) 337.1137.
1
H
19
N
1
S O
1 2
JO061318Y
J. Org. Chem, Vol. 71, No. 18, 2006 7123