Aza-Morita-Baylis-Hillman reaction with ion-supported Ph3P

Article abstract of DOI:10.1016/j.tet.2012.01.034

Various N-tosyl arylimines reacted with methyl vinyl ketone and ethyl vinyl ketone in the presence of ion-supported Ph₃P A and B to give adducts, N-(2′-methylene-3′-oxo-1′-arylbutyl)-4- methylbenzenesulfonamides and N-(2′-methylene-3′-oxo-1′- a

Full text of DOI:10.1016/j.tet.2012.01.034

Tetrahedron 68 (2012) 2319e2325
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Aza-MoritaeBayliseHillman reaction with ion-supported Ph3P
*
Yumi Imura, Naoya Shimojuh, Katsuhiko Moriyama, Hideo Togo
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Various N-tosyl arylimines reacted with methyl vinyl ketone and ethyl vinyl ketone in the presence of ion-
supported Ph3P A and
B
to give adducts, N-(20-methylene-30-oxo-10-arylbutyl)-4-methylbenzene-
Received 20 December 2011
Received in revised form 10 January 2012
Accepted 13 January 2012
sulfonamides and N-(20-methylene-30-oxo-10-arylpentyl)-4-methylbenzenesulfonamides, respectively, in
good yields with high purity by simple diethyl ether extraction of the reaction mixture. Moreover, ion-
supported Ph3P A and B could be repeatedly used for the same reaction to provide the corresponding ad-
ducts while maintaining good yields with high purity.
Available online 26 January 2012
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
N-methyl-N-[4-(diphenyl-phosphino)benzyl]pyrrolidinium
bro-
mide B, and found that these ion-supported Ph3P A and B were
stable under argon gas for long time and could be used for the
halogenation of alcohols, the esterification of carboxylic acids,4a
and the Wittig reaction4b as an equivalent required reagent. We
also found that the quantitatively recovered ion-supported Ph3PO
was regenerated to ion-supported Ph3P A and B, which could be
reused for the same reactions. Here, we would like to report the
aza-MBH reaction of N-tosyl arylimines with vinyl ketones using
ion-supported Ph3P A and B as the catalyst.
The aza-MoritaeBayliseHillman (aza-MBH) reaction with N-
tosyl arylimines with vinyl ketones is a very attractive and impor-
tant tool for CeC bond formation as it provides enriched
b-amino
carbonyl compounds bearing an -exo-methylene group and yields
a
potent and useful building blocks for organic synthesis. Therefore,
the active study for the aza-MBH reaction of N-tosyl arylimines
with vinyl ketones using tertiary amines, phosphines, and chiral
amines and phosphines as the catalyst has been well carried out.1
Generally, the reaction must be performed under mild reaction
conditions, i.e., room temperature, in the presence of 10e20 mol %
catalyst to give products in good yields. However, the reaction
mixture must undergo troublesome purification by column chro-
matography to remove the catalyst. Recently, polymer-supported
diphenylphosphine and DMAP,2a,b and calix[4]arene-supported
diphenylphosphine2c for the aza-MBH reaction were reported to
generate products in good yields, although purification of the fil-
trates by short column chromatography was still required.1g,2 In
view of process chemistry and environmentally benign organic
synthesis, simple experimental procedure and simple isolation of
the desired product are very important. Therefore, we have set our
sights on elucidating the synthetic use of ion-supported reagents,
such as ion-supported PhI,3 ion-supported Ph3P,4 and ion-
supported methyl sulfoxide.5 We expected that the use of an ion-
supported reagent would enable the easy separation of the de-
sired product from the reaction mixture by simple ether extraction
or filtration, and the reuse of the recovered ion-supported reagent
should be possible. Previously, we examined the synthetic use of 4-
(diphenylphosphino)benzyltrimethyl-ammonium bromide A and
2. Results and discussion
First, the optimization of the aza-MBH reaction of N-tosyl 4-
chlorophenylimine with methyl vinyl ketone in the presence of
0.5 equiv of ion-supported Ph3P A or B was carried out at room
temperature, and the results are shown in Tables 1 and 2. CH2Cl2
showed the best reactivity among the solvents used, including THF,
ClCH2CH2Cl, CHCl3, CH3CN, and EtOH (entries 1e6, Tables 1 and 2).
Ion-supported Ph3P (0.5 equiv) was required to give the adduct in
good yield with high purity by simple filtration of the reaction
mixture, and a long reaction time (over 50 h) was required when
the amount of ion-supported Ph3P A or B was reduced to 0.2 equiv
Then, ionic liquids, such as [bmim]PF6, [bmpy]NTf2, [bmim]BF4, and
[emim]OTs, containing ion-supported Ph3P due to reuse of reaction
media containing ion-supported Ph3P A or B, were used under the
same conditions. However, the yield of adduct by extraction with
ether and removal of the solvent from the extract was low (entries
7e10, Tables 1 and 2). On the basis of these results, the aza-MBH
reaction of N-tosyl 4-chlorophenylimine with methyl vinyl ketone
ꢀ
in the presence of both ion-supported Ph3P A or B, and MS 4 A
(w0.1 g) was carried out to provide the adduct in high yields with
ꢀ
high purity (entry 11 in Tables 1 and 2). We believe MS4 A remove
* Corresponding author. Tel./fax: þ81 43 290 2792; e-mail address: togo@facul-
ty.chiba-u.jp (H. Togo).
a trace amount of moisture from IS-Ph3P A and B. On the other
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.01.034

2320
Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
Table 1
hand, when Ph3P, instead of ion-supported Ph3P A, was used under
Optimization of aza-MBH reaction using ion-supported Ph3P A
the same conditions, the adduct was obtained in high yield, al-
though its purity was 60% due to the presence of Ph3P in the filtrate
after the same filtration of the reaction mixture, and the residue
could not be reused at all (entry 12, Table 1).
Based on these results, the aza-MBH reaction of N-tosyl aryli-
mines, such as N-tosyl 4-chlorophenylimine, 4-bromophenylimine,
4-fluorophenylimine,
4-nitrophenylimine,
phenylimine,
4-
methylphenylimine, 4-methoxyphenylimine, 1-naphthylimine,
and 2-thienylimine, with methyl vinyl ketone in the presence of ion-
supported Ph3P A or B was carried out to give the corresponding
adducts in good yields with high purity by simple filtration of the
reaction mixture and removal of the solvent from the filtrate, as
shown inTables 3 and 4 (entries 1e9). There are not much difference
in the reactivity and yield between ion-supported Ph3P A and B.
Unfortunately, the yield of the corresponding adduct in the re-
action of N-tosyl 3-pyridylimine with methyl vinyl ketone in
the presence of ion-supported Ph3P A and B was not high, although
the purity of the adduct was good (entry 10 in Tables 3 and 4).
Then, the same treatment of N-tosyl arylimines, such as N-tosyl
4-chlorophenylimine, 4-bromophenylimine, 4-fluorophenylimine,
4-nitrophenylimine, phenylimine, 4-methylphenylimine, 4-
methoxyphenylimine, 1-naphthylimine, and 2-thienylimine, with
ethyl vinyl ketone in the presence of ion-supported Ph3P A or B was
carried out to give the corresponding adducts in good yields with
high purity again by simple filtration of the reaction mixture and
removal of the solvent from the filtrate, as shown in Tables 5 and 6,
except for N-tosyl 4-methoxylphenylimine. However, the yield of
the adduct in the reaction of ethyl vinyl ketone and N-tosyl 4-
methoxyphenylimine, which has an electron-donating group on
aromatic ring, was improved by increasing the amounts of IS-Ph3P
A or B, and ethyl vinyl ketone (entries 7 in Tables 5 and 6). Then, the
reuse of ion-supported Ph3P A and B in the reaction of N-tosyl 4-
fluorophenylimine with methyl vinyl ketone was carried out and
the results are shown in Table 7. After the addition of diethyl ether
to the first reaction mixture, the obtained mixture was stirred for
30 min at 0 ꢀC. Then, the mixture was filtered to separate ion-
supported Ph3P A or B and the filtrate. After removal of the sol-
vent from the filtrate, the adduct was obtained in high yield with
94% and 95% purities, respectively, and ion-supported Ph3P A or B
was recovered in quantitative yield. Then, the recovered ion-
supported Ph3P A or B was added to a mixture of N-tosyl 4-
fluorophenylimine and methyl vinyl ketone in CH2Cl2, and the
obtained mixture was stirred for 5 h at room temperature again.
After the reaction, diethyl ether was added again to pre-
cipitate the ion-supported Ph3P A or B, and the obtained
mixture was filtered to separate ion-supported Ph3P A or B and
the filtrate containing the adduct, after stirring for 30 min at
Entry
Solvent
Yield (%)
Purity (%)
1
2
3
4
5
6
7
8
THF
CH2C12
C1CH2CH2C1
CHC13
MeCN
64 (34)a
85 (trace)a
77 (14)a
82 (7)a
52
99
75
80
67
36
26
30
d
70 (16)a
52 (20)a (16)b
30 (58)a
42 (38)a
9 (13)a (68)b
56 (36)a
quant.
EtOH
[bmim]PF6
[bmpy]NTf2
[bmim]BF4
[emim]OTs
CH2C12
9
10
11c
12c,d
51
>99
60
CH2C12
99
a
Yield of aldehyde.
Yield of starting material.
MS 4 A was added.
Ph3P was used instead of IS-Ph3P.
b
c
ꢀ
d
Table 2
Optimization of aza-MBH reaction using ion-supported Ph3P B
0
ꢀC. By using this procedure, the adduct was obtained in high
yields with high purity up to the fourth time, and ion-
supported Ph3P A and were recovered in quantitative
yields each time, respectively.
B
Entry
Solvent
Yield (%)
Purity (%)
1
2
3
4
5
6
7
8
THF
CH2C12
C1CH2CH2C1
CHC13
MeCN
10 (trace)a (85)b
85 (trace)a
71 (5)a (trace)b
73 (trace)a
65 (16)a (trace)b
60 (14)a (25)b
20 (53)a (6)b
72 (27)a
5
99
70
70
60
45
d
EtOH
[bmim]PF6
[bmpy]NTf2
[bmim]BF4
[emim]OTs
CH2C12
48
d
9
0 (90)b
10
26 (20)a (49)b
95
d
11c
>99
a
Yield of aldehyde.
b
c
Yield of starting material.
ꢀ
MS 4 A was added.

Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
2321
Table 3
Table 4
Investigation of aza-MBH reaction using ion-supported Ph3P A
Investigation of aza-MBH reaction using ion-supported Ph3P B
Additionally, when O-benzyl N-benzylidinecarbamate was
treated with methyl vinyl ketone in the presence of ion-
supported Ph3P A, the adduct, N-(20-methylene-30-oxo-10-
phenylbutyl)-O-benzyl-carbamate was obtained in good yield
with high purity, as shown in Eq. 1, together with quantitative
recovery of ion-supported Ph3P A.
filtration of the reaction mixture, and the recovered ion-supported
Ph3P A and B could be reused for the same reaction while main-
taining good yield and high purity of the adducts. Thus the present
ion-supported Ph3P A and B are useful recyclable catalysts for aza-
MBH reaction.
On the other hand, the reactions of N-tosyl arylimines with ethyl
acrylate, acrolein, or acrylonitrile in the presence of ion-supported
Ph3P A or B gave the adducts in very low yields.
4. Experimental
4.1. General
3. Conclusion
1H NMR and 13C NMR spectra were obtained with JEOL-JNM-
ECX400, JEOL-JNM-ECS400, and JEOL-JNM-ECA500 spectrometers.
Chemical shifts are expressed in parts per million downfield from
Ion-supported Ph3P A and B could be used as a catalyst for the
reaction of N-tosyl arylimines with vinyl ketones to give the cor-
responding adducts in good yields with high purity by simple
TMS in
d units. Mass spectra were recorded on JMS-T100GCV, JMS-

2322
Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
Table 5
Table 6
Investigation of aza-MBH reaction using ion-supported Ph3P A
Investigation of aza-MBH reaction using ion-supported Ph3P B
HX110, and Thermo LTQ Orbitrap XL spectrometers. IR spectra were
measured with a JASCO FT/IR-4100 spectrometer. Melting points
were determined with a Yamato Melting Point Apparatus Model
MP-21. Silica gel 60 (Kanto Kagaku Co.) was used for column
chromatography.
7.32e7.40 (m, 12H); 13C NMR (CDCl3, TMS)
d
¼52.66 (p), 68.37 (s),
127.43 (q), 128.65 (d, JCeP¼6.7 Hz, t), 129.14 (t), 132.88 (d,
JCeP¼6.7 Hz, t), 133.88 (d, JCeP¼19.6 Hz, t), 133.95 (d, JCeP¼18.6 Hz,
t), 135.86 (d, JCeP¼10.5 Hz, q), 141.50 (d, JCeP¼14.3 Hz, q); 31P NMR
(CDCl3, H3PO4)
C22H25BrNP$1/2CH3OH: C, 62.80%; H, 6.32%; N, 3.25%. Found: C,
d
¼ꢁ4.98; Elemental analysis: calcd for
4.2. Ion-supported Ph3P A and B were prepared by the
previous method4
62.77%; H, 6.09%; N, 3.16%.
4.2.2. N-Methyl-N-[4-(diphenylphosphino)benzyl]pyrroliꢁd1inium bro-
;
1H NMR
4.2.1. 4-(Diphenylphosphino)benzyltrimethylammonium
A. Mp 168e170 ꢀC; IR (neat) 1477, 1433, 822, 745, 697 cmꢁ1
NMR (CDCl3, TMS)
¼3.39 (s, 9H), 5.02 (s, 2H), 7.27e7.30 (m, 2H),
bromide
mide B. Mp 207e209 ꢀC; IR (neat) 1433, 742, 696 cm
;
1H
(CDCl3, TMS)
d¼2.22 (m, 2H), 2.35 (m, 2H), 3.21 (s, 3H), 3.68 (m,
d
2H), 4.03 (m, 2H), 5.08 (s, 2H), 7.26e7.40 (m, 12H), 7.62 (d, J¼2.8 Hz,

Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
2323
Table 7
hexane¼1:2). The ion-supported Ph3P, B was recovered by the
above filtration in 100% yield.
Reuse of ion-supported Ph3P in aza-MBH reaction
4.3.2. N-[10-(400-Chlorophenyl)-20-methylene-30-oxobutyl] 4-
methylbenzenesulfonamide. Mp 109e112 ꢀC (lit.1g mp 112e113 ꢀC);
€
IR (Nujol): 3264 (NeH), 1674 (C]O), 1596, 1492, 1416, 1327, 1281,
1163, 1092, 1055, 1014, 961, 815, 720, 676 cmꢁ1; 1H NMR (500 MHz,
CDCl3):
d
¼2.15 (s, 3H), 2.41 (s, 3H), 5.24 (d, J¼8.9 Hz, 1H), 5.85 (d,
J¼8.9 Hz,1H), 6.06 (s, 1H), 6.09 (s, 1H), 7.04 (d, J¼8.3 Hz, 2H), 7.16 (d,
J¼8.6 Hz, 2H), 7.23 (d, J¼8.0 Hz, 2H), 7.63 (d, J¼8.3 Hz, 2H); 13C NMR
(125 MHz, CDCl3):
d¼21.41 (p), 26.14 (p), 57.94 (s), 127.10 (t), 127.84
(t), 128.41 (t), 128.43 (t), 129.43 (t), 133.26 (q), 137.23 (q), 137.42 (q),
143.42 (q), 146.07 (q), 198.63 (q); HRMS (ESI) calcd for
C18H18O3NClNaS [MþNa]þ: 386.0582. Found: 386.0588.
Reuse
IS-Ph3P A
IS-Ph3P B
Yield (%)
Yield (%)
Purity (%)
Purity (%)
0
97
96
96
98
97
94
95
99
98
97
100
98
100
100
95
95
98
98
95
94
4.3.3. N-[10-(400-Bromophenyl)-20-methylene-30-oxobutyl]-4-
la
methylbenzenesulfonamide. Mp 100e102 ꢀC (lit.1g mp 115e116 ꢀC);
2a
3a
4a
€
IR (Nujol): 3244 (NeH), 1669 (C]O), 1488, 1319, 1121, 1073, 1010,
947, 807, 671 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼2.15 (s, 3H), 2.42
a
(s, 3H), 5.21 (d, J¼8.9 Hz, 1H), 5.77 (d, J¼8.9 Hz, 1H), 6.06 (s, 1H),
6.09 (s, 1H), 6.99 (d, J¼8.3 Hz, 2H), 7.23 (d, J¼8.0 Hz, 2H), 7.32 (d,
J¼8.3 Hz, 2H), 7.63 (d, J¼8.3 Hz, 2H); 13C NMR (125 MHz, CDCl3):
Only N-(4-fluorobenzylidene)-4-methylbenzenesulfonamide, methyl vinyl ke-
ꢀ
tone, and MS 4 A were added.
d
¼21.52 (p), 26.28 (p), 58.60 (s), 121.60 (q), 127.21 (t), 128.12 (t),
2H); 13C NMR (CDCl3, TMS)
d
¼21.21 (s), 47.81 (p), 63.12 (s), 65.58 (s)
128.66 (t), 129.53 (t), 131.53 (t), 137.36 (q), 137.92 (q), 143.53 (q),
145.97 (q), 198.80 (q); HRMS (ESI) calcd for C18H18O3NBrNaS
[MþNa]þ: 430.0080. Found: 430.0083.
128.54 (q), 128.79 (d, JCeP¼7.7 Hz, t), 129.27 (t), 132.70 (d,
JCeP¼6.7 Hz, t), 133.91 (d, JCeP¼20.1 Hz, t), 134.03 (d, JCeP¼18.2 Hz,
t), 136.08 (d, JCeP¼10.5 Hz, q), 141.23 (d, JCeP¼14.4 Hz, q); 31P NMR
4.3.4. N-[10-(400-Fluorophenyl)-20-methylene-30-oxobutyl] 4-
(CDCl3, H3PO4)
d
¼ꢁ5.00; Elemental analysis: calcd for
methylbenzenesulfonamide. Mp
113e118
104e106 C); IR (Nujol): 3252 (NeH), 1669 (C]O), 1598, 1507, 1334,
1220, 1157, 1072, 953, 835, 719, 662 cmꢁ1 1H NMR (500 MHz,
CDCl3):
ꢀC
(lit.1g
mp
C24H27BrNP$1/2H2O: C, 64.15%; H, 6.28%; N, 3.12%. Found: C,
64.09%; H, 6.11%; N, 2.96%.
ꢀ
€
;
d
¼2.16 (s, 3H), 2.41 (s, 3H), 5.25 (d, J¼8.9 Hz, 1H), 5.73 (d,
4.3. Typical procedure for the aza-MBH with ion-supported
Ph3P A or B
J¼8.9 Hz, 1H), 6.07 (s, 1H), 6.10 (s, 1H), 6.88 (dd, J¼8.7, 8.6 Hz, 2H),
7.08 (dd, J¼8.4, 5.3 Hz, 2H), 7.24 (d, J¼8.0 Hz, 2H), 7.64 (d, J¼8.3 Hz,
2H); 13C NMR (125 MHz, CDCl3):
d¼21.50 (p), 26.32 (p), 58.39 (s),
Methyl vinyl ketone (122.0
m
L,1.5 mmol) was added to a solution
115.33 (d, JCeF¼21.6 Hz, t), 126.84 (t), 127.80 (t), 127.87 (d,
JCeF¼2.7 Hz, t), 129.52 (t), 134.64 (q), 137.38 (q), 143.47 (q), 146.24
(q), 162.05 (d, JCeF¼247.1 Hz, q), 198.84 (q); HRMS (ESI) calcd for
C18H18O3NFNaS [MþNa]þ: 370.0875. Found: 370.0884.
of N-(40-fluorobenzylidene)-4-methylbenzenesulfonamide (277.0
mg, 1.0 mmol), catalyst B (220.0 mg, 0.5 mmol) and MS 4 A
ꢀ
(w100 mg) in CH2Cl2 (4 mL). The obtained mixture was stirred for
5 h at room temperature under an argon atmosphere. After the
reaction, diethyl ether (10 mL) was added and the obtained mixture
was stirred for 30 min at 0 ꢀC. After that, the mixture was filtered
and washed with diethyl ether. Removal of the solvent from the
filtrates gave N-[10-(400-fluorophenyl)-20-methylene-30-oxobutyl]-
4-methylbenzenesulfonamide quantitatively with 95% purity,
which was estimated by 1H NMR. Pure N-[10-(400-chlorophenyl)-20-
methylene-30-oxobutyl]-4-methylbenzenesulfonamide was ob-
tained in 100% yield by very short flash column chromatography on
silica gel (AcOEt/hexane¼1:2).Ion-supported Ph3P, B was recovered
by the above filtration in 100% yield.
4.3.5. N-[10-(400-Nitrophenyl)-20-methylene-30-oxobutyl]-4-
methylbenzenesulfonamide. Mp 121e125 ꢀC (lit.1g mp 120e122 ꢀC);
€
IR (Nujol): 3239 (NeH), 1656 (C]O), 1597, 1515, 1376, 1342, 1239,
1158, 1092, 1069, 812, 740, 706, 669 cmꢁ1 1H NMR (500 MHz,
;
CDCl3):
d
¼2.16 (s, 3H), 2.42 (s, 3H), 5.31 (d, J¼8.9 Hz, 1H), 5.83 (d,
J¼8.9 Hz,1H), 6.08 (s, 1H), 6.14 (s, 1H), 7.25 (d, J¼8.3 Hz, 2H), 7.35 (d,
J¼8.9 Hz, 2H), 7.65 (d, J¼8.3 Hz, 2H), 7.08 (d, J¼8.9 Hz, 2H); 13C NMR
(125 MHz, CDCl3):
d¼21.51 (p), 26.18 (p), 58.00 (t), 123.63 (t), 127.18
(t), 127.23 (t), 129.62 (t), 129.68 (s), 137.33 (q), 143.78 (q), 145.40 (q),
146.16 (q), 147.19 (q), 198.76 (q); HRMS (ESI) calcd for C18H17N2O5S
[MꢁH]ꢁ: 373.0864. Found: 373.0863.
4.3.1. Typical reuse of ion-supported Ph3P B. The ion-supported
Ph3P B was dried by a vacuum pump for 2 h at 80 ꢀC. Methyl vi-
4.3.6. N-[20-Methylene-30-oxo-10-phenylbutyl]-4-methyl-benzene-
1g
ꢀ
sulfonamide. Mp 110e114 ꢀC (lit. mp 113e114 C); IR (Nujol): 3257
€
nyl ketone (122.0 mL, 1.5 mmol) was added to a flask containing
catalyst B (220.0 mg, 0.5 mmol), N-(40-fluorobenzylidene)-4-
(NeH), 1664 (C]O), 1597, 1496, 1323, 1304, 1165, 741, 675 cmꢁ1; 1H
ꢀ
methylbenzenesulfon-amide (277.0 mg, 1.0 mmol), and MS 4 A
NMR (500 MHz, CDCl3):
d
¼2.15 (s, 3H), 2.41 (s, 3H), 5.27 (d, J¼8.9 Hz,
(w100 mg) in CH2Cl2 (4 mL). The obtained mixture was stirred for
5 h at room temperature under an argon atmosphere. After the
reaction, diethyl ether (10 mL) was added and the obtained mixture
was stirred for 30 min at 0 ꢀC. After that, the mixture was filtered
and washed with diethyl ether. Removal of the solvent from the
filtrates gave N-[10-(400-fluorophenyl)-20-methylene-30-oxobutyl]-
4-methylbenzenesulfonamide in 98% purity, which was estimated
1H), 5.70 (d, J¼8.9 Hz,1H), 6.09 (s,1H), 6.10 (s,1H), 7.07e7.11 (m, 2H),
7.16e7.21 (m, 3H), 7.23 (d, J¼8.0 Hz, 2H), 7.65 (d, J¼8.3 Hz, 2H); 13C
NMR (125 MHz, CDCl3):
d
¼21.50 (p), 26.31 (p), 58.87 (s), 126.36 (t),
127.26 (t), 127.59 (t), 128.26 (t), 128.49 (t), 129.48 (t), 137.43 (q),
138.82 (q), 143.33 (q), 146.38 (q), 198.82 (q); HRMS (ESI) calcd for
C18H19O3NNaS [MþNa]þ: 352.0968. Found: 352.0978.
1
by H NMR. Pure N-[10-(400-fluorophenyl)-20-methylene-30-oxobu-
tyl]-4-methylbenzenesulfonamide was obtained in 98% yield by
4.3.7. N-[10-(400-Methylphenyl)-20-methylene-30-oxobutyl]-4-
methylbenzenesulfonamide. Mp 116e119 ꢀC (lit.1g mp 118e119 ꢀC);
€
very short flash column chromatography on silica gel (AcOEt/
IR (Nujol): 3281 (NeH), 1682 (C]O), 1595, 1508, 1316, 1264, 1154,

2324
Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
1093, 1073, 957, 936, 826, 813, 661 cmꢁ1
;
1H NMR (500 MHz,
J¼9.2 Hz, 1H), 6.01 (s, 1H), 6.08 (s, 1H), 7.05 (d, J¼8.2 Hz, 2H), 7.17 (d,
CDCl3):
d
¼2.15 (s, 3H), 2.26 (s, 3H), 2.41 (s, 3H), 5.24 (d, J¼8.6 Hz,
J¼8.2 Hz, 2H), 7.23 (d, J¼8.0 Hz, 2H), 7.63 (d, J¼8.0 Hz, 2H); 13C NMR
1H), 5.66 (d, J¼8.6 Hz, 1H), 6.09 (s, 2H), 6.96 (d, J¼8.0 Hz, 2H), 7.00
(100 MHz, CDCl3):
d
¼7.83 (p), 21.59 (p), 31.44 (s), 59.14 (t), 127.32
(d, J¼8.0 Hz, 2H), 7.23 (d, J¼8.0 Hz, 2H), 7.65 (d, J¼8.3 Hz, 2H); 13C
(t), 127.40 (s), 127.81 (t), 128.69 (t), 129.58 (t), 133.46 (q), 137.35 (q),
137.50 (q), 143.48 (q), 145.51 (q), 201.56 (q); HRMS (ESI) calcd for
C19H20O3NClNaS [MþNa]þ: 400.0745. Found: 4000.0739.
NMR (125 MHz, CDCl3):
d¼20.94 (p), 21.48 (p), 26.31 (p), 58.49 (s),
126.29 (t), 127.26 (t), 127.96 (t), 129.16 (t), 129.44 (t), 135.88 (q),
137.33 (q), 137.40 (q), 143.27 (q), 146.54 (q), 198.80 (q); HRMS (ESI)
calcd for C19H21O3NNaS [MþNa]þ: 366.1130. Found: 366.1134.
4.3.13. N-[10-(400-Bromophenyl)-20-methylene-30-oxopentyl]-4-
methylbenzenesulfonamide. Mp 122e125 ꢀC (lit.7 mp 122e124 ꢀC);
4.3.8. N-[10-(400-Methoxyphenyl)-20-methylene-30-oxobutyl]-4-
IR (Nujol): 3254 (NeH), 1673 (C]O), 1597, 1335, 1159, 1074, 1010,
€
methylbenzenesulfonamide. Mp 132e133 ꢀC (lit.1g mp 136e137 ꢀC);
951, 812, 670 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d¼0.93 (t, 3H,
€
IR (Nujol): 3282 (NeH), 1670 (C]O), 1609, 1512, 1325, 1256, 1233,
J¼7.2 Hz), 2.41 (s, 3H), 2.46e2.60 (m, 2H), 5.20 (d, J¼8.9 Hz, 1H),
5.81 (d, J¼8.9 Hz, 1H), 6.01 (s, 1H), 6.08 (s, 1H), 6.99 (d, J¼8.8 Hz,
2H), 7.22 (d, J¼8.2 Hz, 2H), 7.31 (d, J¼8.5 Hz, 2H), 7.62 (d, J¼8.5 Hz,
1178, 1161, 1094, 1030, 962, 834, 814, 723, 666 cmꢁ1 1H NMR
;
(500 MHz, CDCl3):
d
¼2.16 (s, 3H), 2.42 (s, 3H), 3.74 (s, 3H), 5.22 (d,
J¼8.3 Hz, 1H), 5.56 (d, J¼8.3 Hz, 1H), 6.10 (s, 1H), 6.10 (s, 1H), 6.72 (d,
J¼8.9 Hz, 2H), 6.99 (d, J¼8.3 Hz, 2H), 7.24 (d, J¼8.0 Hz, 2H), 7.65 (d,
2H); 13C NMR (100 MHz, CDCl3):
d
¼7.84 (p), 21.60 (p), 31.45 (s),
59.14 (t),121.68 (t),127.32 (t),127.42 (s), 128.20 (t),129.60 (t), 131.65
(q), 137.59 (q), 138.14 (q), 143.60 (q), 145.57 (q), 201.63 (q); HRMS
(ESI) calcd for C19H20O3NBrNaS [MþNa]þ: 444.0239. Found:
430.0233.
J¼8.3 Hz, 2H); 13C NMR (125 MHz, CDCl3):
¼21.51 (p), 26.38 (p),
d
55.20 (p), 58.30 (s), 113.86 (t), 127.29 (t), 127.67 (t), 127.83 (t), 129.49
(t), 130.93 (q), 137.40 (q), 143.31 (q), 146.62 (q), 158.97 (q), 198.88
(q); HRMS (ESI) calcd for C19H21O4NNaS [MþNa]þ: 382.1075.
Found: 382.1084.
4.3.14. N-[10-(400-Fluorophenyl)-20-methylene-30-oxopentyl]-4-
methylbenzenesulfonamide. Mp 113e115 ꢀC (lit.7 mp 111e112 ꢀC); IR
4.3.9. N-[20-Methylene-10-(naphthalen-100-yl)-30-oxobutyl]-4-
(Nujol): 3294 (NeH), 1670 (C]O), 1597, 1508, 1408, 1344, 1307,
€
methylbenzenesulfonamide. Mp 118e120 ꢀC (lit.6 mp 119e120 ꢀC); IR
1212, 1161, 1094, 1072, 954, 921, 866, 814, 673 cmꢁ1 1H NMR
;
€
(Nujol): 3274 (NeH),1678 (C]O),1596,1508,1320,1286,1154,1093,
(500 MHz, CDCl3):
d
¼0.94 (t, J¼7.2 Hz, 3H), 2.41 (s, 3H), 2.42e2.60
1063, 949, 779, 670 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d¼2.22 (s, 3H),
(m, 2H), 5.24 (d, J¼8.9 Hz, 1H), 5.69 (d, J¼8.9 Hz, 1H), 6.01 (s, 1H),
6.08 (s, 1H), 6.88 (dd, J¼8.8, 8.6 Hz, 2H), 7.08 (dd, J¼8.8, 4.6 Hz, 2H),
7.23 (d, J¼7.7 Hz, 2H), 7.64 (d, J¼7.7 Hz, 2H); 13C NMR (100 MHz,
2.42 (s, 3H), 5.17 (d, J¼7.2 Hz, 1H), 6.20 (d, J¼7.2 Hz, 1H), 6.22 (s, 1H),
6.27 (s,1H), 7.20 (d, J¼8.0 Hz, 2H), 7.25e7.36 (m, 3H), 7.44 (t, J¼7.9 Hz,
1H), 7.72 (d, J¼8.6 Hz, 2H), 7.64 (d, J¼8.3 Hz, 2H), 7.79 (dd, J¼1.3,
CDCl3):
d
¼7.76 (p), 21.47 (p), 31.39 (s), 58.88 (t), 115.43 (d,
8.2 Hz,1H); 13C NMR (125 MHz, CDCl3):
d
¼21.64 (p), 26.48 (p), 53.46
JCeF¼22.0 Hz, t), 127.14 (t), 127.34 (t), 128.19 (d, JCeF¼7.7 Hz, t),
129.58 (t), 134.71 (d, JCeF¼3.7 Hz, t), 137.54 (q), 143.42 (q), 145.76
(q), 161.94 (d, JCeF¼247.1 Hz, q), 201.59 (q); HRMS (ESI) calcd for
C19H20O3NFNaS [MþNa]þ: 384.1040. Found: 384.1026.
(s), 123.01 (t), 125.00 (t), 125.09 (t), 125.94 (t), 126.65 (t), 127.60 (t),
128.00 (t), 128.82 (t), 129.05 (t), 129.65 (t), 130.45 (q), 134.01 (q),
134.64 (q), 136.99 (q), 143.61 (q), 147.50 (q), 198.58 (q); HRMS (ESI)
calcd for C22H21O3NNaS [MþNa]þ: 402.1129. Found: 402.1134.
4.3.15. N-[20-Methylene-10-(400-nitrophenyl)-30-oxopentyl]-4-
4.3.10. N-[20-Methylene-30-oxo-1-(thiophen-200-yl)butyl]-4-
methylbenzenesulfonamide. Mp 147e150 ꢀC (lit.7 mp 147e149 ꢀC);
methylbenzenesulfonamide. Mp 107e108 ꢀC (lit.2c mp 106e107 ꢀC);
IR (Nujol): 3283 (NeH), 1671 (C]O), 1597, 1516, 1206, 1162, 1075,
€
IR (Nujol): 3215 (NeH), 1671 (C]O), 1596, 1507, 1319, 1229, 1159,
813, 721 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d¼0.93 (t, J¼7.3 Hz, 3H),
€
1093, 1071, 983, 925, 815, 721, 671 cmꢁ1
;
1H NMR (500 MHz,
2.41 (s, 3H), 2.42e2.59 (m, 2H), 5.33 (d, J¼9.4 Hz, 1H), 5.96 (d,
J¼9.4 Hz,1H), 6.04 (s, 1H), 6.13 (s, 1H), 7.24 (d, J¼8.2 Hz, 2H), 7.35 (d,
J¼8.9 Hz, 2H), 7.64 (d, J¼8.2 Hz, 2H), 8.02 (d, J¼8.9 Hz, 2H); 13C NMR
CDCl3):
d¼2.19 (s, 3H), 2.42 (s, 3H), 5.45 (d, J¼9.2 Hz, 1H), 5.87 (d,
J¼9.2 Hz, 1H), 6.08 (s, 1H), 6.09 (s, 1H), 6.69 (dd, J¼1.1, 3.3 Hz, 1H),
6.83 (dd, J¼3.3, 5.1 Hz, 1H), 7.12 (dd, J¼1.2, 5.1 Hz, 1H), 7.26 (d,
J¼7.7 Hz, 2H), 7.68 (d, J¼8.3 Hz, 2H); 13C NMR (125 MHz, CDCl3):
(100 MHz, CDCl3):
d
¼7.77 (p), 21.59 (p), 31.35 (s), 59.36 (t), 123.71
(t), 126.46 (t),127.27 (t), 127.28 (t), 128.42 (s), 129.69 (t),137.54 (q),
143.87 (q), 144.98 (q), 146.39 (q), 201.53 (q); HRMS (ESI) calcd for
C19H20N2 O5NaS [MþNa]þ: 411.0985. Found: 411.0982.
d
¼21.53 (p), 26.32 (p), 55.72 (s), 124.94 (t), 125.31 (t), 126.94 (t),
127.31 (t), 128.47 (t), 129.53 (t), 137.36 (q), 143.05 (q), 143.46 (q),
145.88 (q), 198.84 (q); HRMS (ESI) calcd for C16H17O3NNaS2
[MþNa]þ: 358.0533. Found: 358.0542.
4.3.16. N-[20-Methylene-30-oxo-10-phenylpentyl]-4-methyl-
benzenesulfonamide. Mp 87e90 ꢀC (lit. mp 84e86 ꢀC); IR (Nujol):
7
€
4.3.11. N-[20-Methylene-30-oxo-1-(pꢀyridin-300-yl)butyl]-4-
3281 (NeH), 1677 (C]O), 1599, 1495, 1453, 1378, 1334, 1161, 1092,
methylbenzenesulfonamide. Mp 105e109 C; IR (Nujol): 1676 (C]
1066, 1029, 949, 815, 698, 669 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
€
O), 1593, 1428, 1323, 1303, 1266, 1182, 1155, 1093, 1071, 1049, 1030,
d
¼0.93 (t, J¼7.3 Hz, 3H), 2.40 (s, 3H), 2.43e2.59 (m, 2H), 5.27 (d,
984, 954, 850, 817, 710, 660 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
J¼8.7 Hz, 1H), 5.68 (d, J¼8.7 Hz, 1H), 6.04 (s, 1H), 6.09 (s, 1H),
7.08e7.11 (m, 2H), 7.16e7.26 (m, 3H), 7.23 (d, J¼8.0 Hz, 2H), 7.65 (d,
d
¼2.15 (s, 3H), 2.39 (s, 3H), 5.27 (br, 1H), 5.94 (br, 1H), 6.09 (s, 1H),
6.12 (s, 1H), 7.13 (dd, J¼8.2, 4.8 Hz, 1H), 7.22 (d, J¼8.2 Hz, 2H), 7.52
(dt, J¼8.2, 1.7 Hz, 1H), 7.63 (d, J¼8.2 Hz, 2H), 8.29 (d, J¼1.7 Hz, 1H),
J¼8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼7.87 (p), 21.59 (p),
d
31.45 (s), 59.42 (t), 126.43 (t), 126.97 (s), 127.38 (s), 127.66 (t), 128.60
(t), 129.55 (t), 137.67 (q), 139.03 (q), 143.40 (q), 146.00 (q), 201.64
(q); HRMS (APPI) calcd for C19H20O3NS [MꢁH]ꢁ: 342.1169. Found:
342.1173.
8.40 (dd, J¼4.8, 1.7 Hz, 1H); 13C NMR (125 MHz, CDCl3):
¼21.60 (p),
d
26.31 (p), 57.45 (t),123.38 (t),127.29 (t),129.28 (s),129.72 (t),134.24
(t),134.73 (q),137.49 (q),143.72 (q),145.66 (q), 148.06 (t), 148.89 (t),
198.88 (q); HRMS (ESI) calcd for C17H19O3N2S [MþH]þ: 331.111.
Found: 331.1099.
4.3.17. N-[20-Methylene-10-(400-methylphenyl)-30-oxopentyl]-4-
methylbenzenesulfonamide. Mp 116e119 ꢀC; IR (Nujol): 3289
€
4.3.12. N-[10-(400-Chlorophenyl)-20-methylene-30-oxopentyl]-4-
(NeH), 1676 (C]O), 1598, 1513, 1160, 1075, 1022, 953, 814,
methylbenzenesulfonamide. Mp 111e113 ꢀC (lit.7 mp 112e113 ꢀC); IR
721 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d¼0.93 (t, 3H, J¼7.3 Hz), 2.41
€
(Nujol): 3278 (NeH), 1675 (C]O), 1597, 1159, 1072, 1013, 952, 813,
(s, 3H), 2.43e2.64 (m, 2H), 5.23 (d, J¼8.5 Hz, 1H), 5.56 (d, J¼8.5 Hz,
1H), 6.05 (s, 1H), 6.09 (s, 1H), 6.97 (d, J¼8.2 Hz, 2H), 7.01 (d,
J¼8.2 Hz, 2H), 7.23 (d, J¼8.5 Hz, 2H), 7.65 (d, J¼8.5 Hz, 2H); 13C NMR
721, 671 cmꢁ1; 1H NMR (400 MHz, CDCl3):
2.41 (s, 3H), 2.43e2.60 (m, 2H), 5.23 (d, J¼9.2 Hz, 1H), 5.69 (d,
d
¼0.95 (t, 3H, J¼7.3 Hz),

Y. Imura et al. / Tetrahedron 68 (2012) 2319e2325
2325
(125 MHz, CDCl3):
d
¼7.76 (p), 20.96 (p), 21.48 (p), 31.36 (s), 59.03
7.55 (dt, J¼8.0, 2.1 Hz, 1H), 7.65 (d, J¼8.0 Hz, 2H), 8.31 (d, J¼2.1 Hz,
(t), 126.25 (t), 126.64 (s), 127.30 (t), 129.20 (t), 129.43 (t), 136.00 (q),
137.34 (q), 137.55 (q), 143.26 (q), 146.05 (q), 201.52 (q); HRMS (ESI)
calcd for C20H23O3NNaS [MþNa]þ: 380.1291. Found: 380.1283.
1H), 8.43 (dd, J¼4.8, 2.1 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼7.80
d
(p), 21.59 (p), 31.39 (s), 57.96 (t), 123.39 (t), 127.20 (t), 127.23 (s),
127.29 (t), 128.03 (t), 129.68 (q), 132.01 (q), 134.14 (q), 137.55 (q),
145.04 (t), 148.90 (t), 223.97 (q); HRMS (ESI) calcd for C18H21O3N2S
[MþH]þ: 345.1267. Found: 345.1259.
4.3.18. N-[10-(400-Methoxyphenyl)-20-methylene-30-oxopentyl]-4-
methylbenzenesulfonamide. Mp 137e139 ꢀC; IR (Nujol): 3281
€
(NeH), 1672 (C]O), 1600, 1512, 1329, 1163, 1093, 1030, 956, 814,
4.3.22. N-(2-Methylene-3-oxo-1-phenylbutyl)-O-benzyl-carbama-
724 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d¼0.94 (t, J¼8.4 Hz), 2.41 (s,
te. Mp 81e82 C; IR (Nujol): 3322 (NeH), 1684 (C]O), 1283, 1158,
ꢀ
€
3H), 2.43e2.63 (m, 2H), 3.74 (s, 3H), 5.22 (d, J¼8.5 Hz, 1H), 5.52 (d,
J¼8.5 Hz,1H), 6.04 (s,1H), 6.08 (s,1H), 6.73 (d, J¼9.1 Hz, 2H), 7.00 (d,
J¼8.7 Hz, 2H), 7.25 (d, J¼8.3 Hz, 2H), 7.65 (d, J¼8.5 Hz, 2H); 13C NMR
1117, 1043, 965, 916, 866, 721 cmꢁ1 1H NMR (500 MHz, CDCl3):
;
d
¼2.29 (s, 3H), 5.11 (s, 2H), 5.71 (d, J¼8.6 Hz, 1H), 5.82 (br s,
J¼8.6 Hz, 1H), 6.13 (s, 1H), 6.21 (s, 1H), 7.19e7.38 (m, 10H); 13C NMR
(125 MHz, CDCl3):
d
¼7.8 (p), 21.59 (p), 31.49 (s), 55.31 (p), 58.75 (t),
(100 MHz, CDCl3):
d¼26.67 (p), 56.90 (t), 67.04 (s), 126.48 (t), 127.38
113.97 (t), 127.39 (t), 127.75 (t), 127.98 (t), 129.56 (t), 131.15 (q),
137.61 (q), 143.37 (q), 146.24 (q), 159.06 (q), 201.69 (q); HRMS (ESI)
calcd for C20H23O4NNaS [MþNa]þ: 396.1240. Found: 396.1228.
(s), 127.57 (t), 128.24 (t), 128.62 (t), 128.66 (t), 136.44 (q), 139.91 (q),
147.59 (q), 155.69 (q), 199.01 (q); HRMS (ESI) calcd for C19H20O3N
[MþH]þ: 310.1438. Found: 310.1434.
4.3.19. N-[20-Methylene-10-(naphthalen-100-yl)-30-oxopentyl]-4-
methylbenzenesulfonamide. Mp 119e120 ꢀC; IR (Nujol): 3269
€
Acknowledgements
(NeH), 1666 (C]O), 1597, 1336, 1157, 1092, 1070, 1024, 933, 804,
780, 721, 670 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼0.94 (t, J¼7.3 Hz,
Financial support in the form of a Grant-in-Aid for Scientific
Research (No. 20550033) from the Ministry of Education, Culture,
Sports, Science, and Technology in Japan, and Iodine Research
Project in Chiba University, is gratefully acknowledged.
3H), 2.42 (s, 3H), 2.47e2.71 (m, 2H), 5.14 (d, J¼7.1 Hz, 1H), 6.17 (s,
1H), 6.21 (d, J¼7.1 Hz, 1H), 6.25 (s, 1H), 7.20 (d, J¼8.5 Hz, 2H),
7.25e7.35 (m, 3H), 7.44 (t, J¼8.0 Hz, 1H), 7.64 (d, J¼8.2 Hz, 2H), 7.72
(dd, J¼3.6, 4.8 Hz, 1H), 7.64 (d, J¼8.3 Hz, 2H); 13C NMR (100 MHz,
CDCl3):
d
¼7.92 (p), 21.59 (p), 31.54 (s), 53.71 (t), 122.99 (t), 124.96
References and notes
(t), 125.07 (t), 125.92 (t), 126.47 (s), 126.64 (t), 127.57 (t), 128.80 (t),
129.00 (t), 129.61 (t), 130.45 (q), 134.01 (q), 134.70 (q), 137.08 (q),
143.63 (q),147.08 (q), 201.31 (q); HRMS (ESI) calcd for C23H23O3N-
NaS [MþNa]þ: 416.1291. Found: 416.1285.
1. (a) Basavaiah, D.; Rao, P. D.; Hyma, R. S. Tetrahedron 1996, 52, 8001; (b) Ciganek,
E. Org. React. 1997, 51, 201; (c) Shi, M.; Xu, Y. Chem. Commun. 2001, 1876; (d)
Basavaiah, D.; Rao, A. J.; Satyanarayana, T. Chem. Rev. 2003, 103, 811; (e) Shi, M.;
Xu, Y. J. Org. Chem. 2003, 68, 4784; (f) Shi, M.; Zhao, G. Adv. Synth. Catal. 2004,
346, 1205; (g) Zhao, L.; He, H. S.; Shi, M.; Toy, P. H. J. Comb. Chem. 2004, 6, 680; (h)
Shi, M.; Li, C. Tetrahedron: Asymmetry 2005, 16, 1385; (i) Ito, K.; Nishida, K.;
Gotanda, T. Tetrahedron Lett. 2007, 48, 6147; (j) Basavaiah, D.; Rao, K. V.; Reddy,
R. J. Chem. Soc. Rev. 2007, 36, 1581; (k) Shi, Y.; Shi, M. Eur. J. Org. Chem. 2007,
2905; (l) Shi, Y.; Shi, M. Adv. Synth. Catal. 2007, 349, 2129; (m) Lei, Z.; Ma, G.; Shi,
M. Eur. J. Org. Chem. 2008, 3817; (n) Qi, M.; Ai, T.; Shi, M.; Li, G. Tetrahedron 2008,
64, 1181; (o) Guan, X.; Jiang, Y.; Shi, M. Eur. J. Org. Chem. 2008, 2150; (p) Takizawa,
S.; Horii, A.; Sasai, H. Tetrahedron: Asymmetry 2010, 21, 891; (q) Decierck, V.;
Martinez, J.; Lamaty, F. Chem. Rev. 2009, 109, 1; (r) Wei, Y.; Shi, M. Acc. Chem. Res.
2010, 43, 1005; (s) Clary, K. N.; Parvez, M.; Back, T. G. J. Org. Chem. 2010, 75, 3751;
(t) Takizawa, S.; Kiriyama, K.; Ieki, K.; Sasai, H. Chem. Commun. 2011, 9227; (u)
Regiani, T.; Santos, V. G.; Godoi, M. N.; Vaz, B. G.; Eberlin, M. N.; Coelho, F. Chem.
Commun. 2011, 6593.
2. (a) Huang, J.; Shi, M. Adv. Synth. Catal. 2003, 345, 953; (b) Zhao, L.; Kwong, C. K.;
Shi, M.; Toy, P. H. Tetrahedron 2005, 61, 12026; (c) Zhong, W.; Zheng, Y.; Zhou, J.;
Shen, Y. Synlett 2010, 3057.
3. (a) Akiike, J.; Yamamoto, Y.; Togo, H. H. Synlett 2007, 2168; (b) Ishiwata, Y.; Togo,
H. Tetrahedron Lett. 2009, 50, 5354; (c) Kawano, Y.; Togo, H. Tetrahedron 2009, 65,
6251.
4. (a) Imura, Y.; Shimojuh, N.; Togo, H. Tetrahedron 2010, 66, 3421; (b) Shimojuh, N.;
Imura, Y.; Moriyama, K.; Togo, H. Tetrahedron 2011, 67, 951.
5. Tsuchiya, D.; Moriyama, K.; Togo, H. Synlett 2011, 2701.
4.3.20. N-[20-Methylene-30-oxo-10-(thiophen-200-yl)-pentyl]-4-
methylbenzenesulfonamide. Mp 107e108 ꢀC; IR (Nujol): 3280
€
(NeH), 1676 (C]O), 1434, 1411, 1377, 1334, 1306, 1161, 1093, 1070,
815, 756, 706, 668 cmꢁ1
;
1H NMR (500 MHz, CDCl3):
d
¼0.98 (t,
J¼7.3 Hz, 3H), 2.41 (s, 3H), 2.42e2.63 (m, 2H), 5.45 (d, J¼9.4 Hz, 1H),
5.89 (d, J¼9.4 Hz, 1H), 6.03 (s, 1H), 6.08 (s, 1H), 6.70 (dd, J¼1.2,
3.4 Hz, 1H), 6.82 (dd, J¼3.4, 5.1 Hz, 1H), 7.11 (dd, J¼1.2, 5.2 Hz, 1H),
7.25 (d, J¼7.7 Hz, 2H), 7.68 (d, J¼8.2 Hz, 2H); 13C NMR (100 MHz,
CDCl3):
d
¼7.80 (p), 21.60 (p), 31.48 (s), 56.26 (t), 124.99 (t), 125.35
(t), 127.05 (t), 127.23 (s), 127.42 (t), 129.53 (t), 137.89 (q), 143.10 (q),
143.46 (q), 145.40 (q), 201.52 (q); HRMS (ESI) calcd for
C17H19O3NNaS2 [MþNa]þ: 372.0699. Found: 372.0688.
4.3.21. N-[20-Methylene-30-oxo-10-(pyridin-300-yl)pentyl[-4-
ꢀ
€
methylbenzenesulfonamide. Mp 106e110 C; IR (Nujol): 1688 (C]
O), 1594, 1327, 1180, 1153, 1091, 1067, 1028, 946, 855, 807, 719 cmꢁ1
1H NMR (500 MHz, CDCl3):
;
d
¼0.94 (t, J¼7.3 Hz, 3H), 2.41 (s, 3H),
6. Matsui, K.; Tanaka, K.; Horii, A.; Takizawa, S.; Sasai, H. Tetrahedron: Asymmetry
2006, 17, 578.
7. Shi, M.; Chen, L.; Li, C. J. Am. Chem. Soc. 2005, 127, 3790.
2.43e2.62 (m 2H), 5.28 (d, J¼9.2 Hz, 1H), 5.90 (d, J¼9.2 Hz, 1H), 6.06
(s,1H), 6.12 (s,1H), 7.16 (dd, J¼8.0, 4.8 Hz,1H), 7.24 (d, J¼8.0 Hz, 2H),