An unexpected highly stereoselective double aza-Baylis - Hillman reaction of sulfonated imines with phenyl vinyl ketone

Article abstract of DOI:10.1021/jo034114f

The aza-Baylis - Hillman reaction of N-sulfonated imine with phenyl vinyl ketone gave the double aza-Baylis - Hillman adduct in good yields with excellent stereoselectivities in the presence of Lewis base 1,4-diazabicyclo[2.2.2] octane.

Full text of DOI:10.1021/jo034114f

An Un exp ected High ly Ster eoselective Dou ble Aza -Ba ylis-Hillm a n
Rea ction of Su lfon a ted Im in es w ith P h en yl Vin yl Keton e
Min Shi* and Yong-Mei Xu
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Science, 354 Fenglin Lu, Shanghai 200032, China
mshi@pub.sioc.ac.cn
Received J anuary 28, 2003
The aza-Baylis-Hillman reaction of N-sulfonated imine with phenyl vinyl ketone gave the double
aza-Baylis-Hillman adduct in good yields with excellent stereoselectivities in the presence of Lewis
base 1,4-diazabicyclo[2.2.2]octane.
SCHEME 1
Great progress has been made in the execution of the
Baylis-Hillman reaction,1 for which a catalytic asym-
metric version has been published,2 since Baylis and
Hillman first reported in 1972 the reaction of acetalde-
hyde with ethyl acrylate and acrylonitrile in the presence
of a catalytic amount of 1,4-diazabicyclo[2.2.2]octane
(DABCO).3 However, during our own investigation of this
simple and useful reaction,4 we found that in the reaction
of arylaldehydes with methyl vinyl ketone (MVK) cata-
lyzed by DABCO, the reaction products are not simple
as those reported before. For example, using p-nitrobenz-
aldehyde (1.0 equiv) and MVK (2.0 equiv) as substrates
in the presence of catalytic amounts of DABCO (0.1
equiv) in DMF or DMSO, we found that besides the
normal Baylis-Hillman product a double Baylis-Hill-
man reaction product was also formed at the same time
as a 2:3 mixture of syn- and anti-isomers.5 The substitu-
ent effects on the benzene ring of arylaldehydes have also
been extensively examined.
* To whom correspondence should be addressed. Fax: 86-21-
64166128.
(1) (a) Ciganek, E. Org. React. 1997, 51, 201. (b) Basavaiah, D.; Rao,
P. D.; Hyma, R. S. Tetrahedron 1996, 52, 8001. (c) Drewes, S. E.; Roos,
G. H. P. Tetrahedron 1988, 44, 4653. (d) Brzezinski, L. J .; Rafel, S.;
Leahy, J . M. J . Am. Chem. Soc. 1997, 119, 4317. (e) Miyakoshi, T.;
Saito, S. Nippon Kagaku Kaishi 1983, 1623; Chem. Abstr. 1984, 100,
156191g. (f) Marko, I. E.; Giles, P. R.; Hindley, N. J . Tetrahedron 1997,
53, 1015. (g) Richter, H.; J ung, G. Tetrahedron Lett. 1998, 39, 2729.
(h) Barrett, A. G. M.; Cook, A. S.; Kamimura, A. Chem. Commun. 1999,
2533. (i) Kunidig, E. P.; Xu, L. H.; Romanens, P.; Bernardinelli, G.
Tetrahedron Lett. 1993, 34, 7049. (j) Aggarwal, V. K.; Mereu, A.;
Tarver, G. J .; McMague, R. J . Org. Chem. 1998, 63, 7183. (k)
Kawamura, M.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 1539. (l)
Li, G.-G.; Wei, H.-X.; Gao, J .-J .; Caputo, T. D. Tetrahedron Lett. 2000,
41, 1. (m) Li, G.-G.; Gao, J .-J .; Wei, H.-X.; Enright, M. Org. Lett. 2000,
2, 617 and references therein. (o) Iwamura, T.; Fujita, M.; Kawakita,
T.; Kinoshita, S.; Watanabe, S.-I.; Kataoka, T. Tetrahedron 2001, 57,
8455 and references therein.
(2) (a) Iwabuchi, Y.; Nakatani, M.; Yokoyama, N.; Hatakeyama, S.
J . Am. Chem. Soc. 1999, 121, 10219. (b) Langer, P. Angew. Chem.,
Int. Ed. 2000, 39, 3049.
(3) (a) Baylis, A. B.; Hillman, M. E. D. Ger. Offen. 2,155,113, 1972;
Chem. Abstr. 1972, 77, 34174q. Hillman, M. E. D.; Baylis, A. B. U.S.
Patent 3,743,669, 1973. (b) Morita, K.; Suzuki, Z.; Hirose, H. Bull.
Chem. Soc. J pn. 1968, 41, 2815.
Two plausible mechanisms for the formation of the
double Baylis-Hillman adduct can be speculated which
have been elucidated in Scheme 1. The first mechanism
is the Michael addition of enolate derived from DABCO
and MVK to the Baylis-Hillman adduct, and the second
is the aldol condensation reaction of enolate derived from
DABCO and MVK (a MVK dimer type enolate) with the
substrate.
This interesting result stimulated us to further exam-
ine the Baylis-Hillman reaction of the other substrates
with R,â-unsaturated ketone because we attempt to find
a new version of the Baylis-Hillman reaction in which
the double Baylis-Hillman reaction product can be
exclusively formed with high stereoselectivity. Herein we
report an unprecedented highly stereoselective double
aza-Baylis-Hillman reaction of N-sulfonated imine with
phenyl vinyl ketone (PVK).
(4) (a) Shi, M.; J iang, J .-K.; Feng, Y.-S. Org. Lett. 2000, 2, 2397. (b)
Shi, M.; Feng, Y.-S. J . Org. Chem. 2001, 66, 406 and references therein.
(5) (a) Shi, M.; Li, C.-Q.; J iang, J .-K. Chem. Commun. 2001, 833.
(b) Shi, M.; Li, C.-Q.; J iang, J .-K. Tetrahedron 2003, 59, 1183.
10.1021/jo034114f CCC: $25.00 © 2003 American Chemical Society
Published on Web 05/17/2003
4784
J . Org. Chem. 2003, 68, 4784-4790

Double Aza-Baylis-Hillman Reaction of Imines with PVK
SCHEME 2
TABLE 1. Lew is Ba se Effect in th e Aza -Ba ylis-Hillm a n
Rea ction of Su lfon a ted Im in e w ith P VK
yielda (%)
Lewis
base
time
(h)
entry
1a
2a
b
1
2
3
4
5
PPh3
1.0
0.2
0.1
5.5
5.5
92
20
Ph2PMeb
50
30
65
50
b
PhPMe2
DABCOb
DABCOc
a
Isolated yields. b The molar ratio of sulfonated imine with PVK
is 0.5:0.75. c The molar ratio of sulfonated imine with PVK is
0.5:0.5.
Resu lts a n d Discu ssion
During our examination of aza-Baylis-Hillman reac-
tions using N-sulfonated imine as the substrate,6,7 we
found that a Lewis base catalyst played a very important
role in the aza-Baylis-Hillman reaction of N-sulfonated
imine (0.5 mmol) with PVK (0.75 mmol) (Scheme 2, Table
1). Using triphenylphosphine (10 mol %) as a Lewis base,
the corresponding normal aza-Baylis-Hillman adduct 1a
was obtained as a sole product in good yield (Table 1,
entry 1). Lewis base Ph2PMe (10 mol %) gave 1a and the
double aza-Baylis-Hillman adduct 2a at the same time
in 20% and 50% yields, respectively (Table 1, entry 2).
In addition, the stronger Lewis base PhPMe2 gave the
aza-Baylis-Hillman adduct exclusively in low yield along
with many unidentified products (Table 1, entry 3). While
using DABCO (10 mol %) as a Lewis base, we delightfully
found that the double aza-Baylis-Hillman adduct 2a was
formed exclusively in good yield (Table 1, entry 4). The
molar ratio of N-sulfonated imine with PVK does not
affect the reaction product because, in the presence of
N-sulfonated imine (0.5 mmol) and PVK (0.5 mmol) (N-
sulfonated imine:PVK ) 1:1), the double aza-Baylis-
Hillman adduct was also exclusively obtained in 50%
yield under the same conditions (Table 1, entry 5).
F IGURE 1. ORTEP drawing of 2a .
TABLE 2. Aza -Ba ylis-Hillm a n Rea ction of Su lfon a ted
Im in e w ith P VK in THF in th e P r esen ce of Lew is Ba se
P P h 3
time
(h)
yield of
entry
Arb
1a (%)
1
2
3
4
5
6
7
8
p-MeOC6H4
p-FC6H4
10
1b, 75
1c, 93
1d , 89
1e, 84
1f, 87
1g, 84
1h , 99
1i, 68
0.5
1.0
1.0
0.5
2.5
3
p-ClC6H4
p-BrC6H4
2,3-Cl2C6H3
p-MeC6H4
m-MeC6H4
p-EtC6H4
6.5
a
Isolated yields. b The molar ratio of sulfonated imine with PVK
is 0.5:0.75.
As can be seen from Table 2, the other N-sulfonated
imines (0.5 mmol) can react with PVK (0.75 mmol)
smoothly in the presence of Lewis base PPh3 to give the
corresponding normal aza-Baylis-Hillman adducts 1b-h
in high yields (Table 2). For substrates having an
electron-withdrawing group on the benzene ring, the
reaction proceeded very well to give 1 in high yields
within shorter reaction time (Table 2, entries 3-6).
On the other hand, if using DABCO as a Lewis base,
in all cases the corresponding double aza-Baylis-Hillman
adducts 2 were obtained exclusively as a sole product
with the anti-configuration (Table 3). To obtain 2 in
higher yields, 3 equiv of PVK was employed in all cases
1
Moreover, on the basis of the H and 13C NMR spectro-
scopic data and X-ray analysis, we are pleased to find
that, in this aza-Baylis-Hillman reaction, the double aza-
Baylis-Hillman reaction product 2a was formed stereo-
selectively in the anti-configuration (Figure 1).8
In Tables 2 and 3, we summarize the results of the
aza-Baylis-Hillman reaction of N-sulfonated imines with
PVK in the presence of Lewis base PPh3 and DABCO,
respectively.
(6) (a) Shi, M.; Xu, Y.-M. Chem. Commun. 2001, 1876. (b) Shi, M.;
Xu, Y.-M. Eur. J . Org. Chem. 2002, 696. (c) Shi, M.; Xu, Y.-M.; Zhao,
G.-L.; Wu, X.-F. Eur. J . Org. Chem. 2002, 3666. (d) Shi, M.; Zhao, G.-
L. Tetrahedron Lett. 2002, 43, 4499.
(7) For previous reports related to the aza-Baylis-Hillman reaction
of methyl acrylate with sulfonated imines, please see: (a) Perlmutter,
P.; Teo, C. C. Tetrahedron Lett. 1984, 25, 5951. (b) Takagi, M.;
Yamamoto, K. Tetrahedron 1991, 47, 8869. For previous reports related
to the aza-Baylis-Hillman reaction of MVK with imine generated in
situ, please see: (c) Bertenshow, S.; Kahn, M. Tetrahedron Lett. 1989,
30, 2731. (d) Balan, D.; Adolfsson, H. J . Org. Chem. 2002, 67, 2329
and references therein. The aza-Baylis-Hillman reaction of sulfonated
imines with PVK has not been examined before.
(8) The X-ray data of 2a have been deposited with Cambridge
Crystallographic Data Centre with the number 194351: empirical
formula, C32H29O4NS; formula weight, 523.62; crystal color (habit),
colorless (prismatic); crystal dimensions, 0.20 × 0.20 × 0.30 mm;
crystal system, monoclinic; lattice type, primitive; lattice parameters,
a ) 12.3996(8) Å, b ) 18.3652(5) Å, c ) 12.3047(8) Å, R ) 90°, â )
90.9440(10)°, γ ) 90°, V ) 2801.7(3) Å3; space group, P2(1)/c; Z value,
4; Dcalcd ) 1.241 g/cm3; F000 ) 1104; µ(Mo KR) ) 1.98 cm-1; residuals,
R ) 0.0566, Rw ) 0.0930.
J . Org. Chem, Vol. 68, No. 12, 2003 4785

Shi and Xu
TABLE 3. Aza -Ba ylis-Hillm a n Rea ction of Su lfon a ted
Im in e w ith P VK in THF in th e P r esen ce of Lew is Ba se
DABCO
yield of
F IGURE 2. Zwitterion species in the Baylis-Hillman reac-
tion.
time
(h)
2a (%)
entry
Arb
C6H5
m-MeC6H4
p-MeC6H4
p-MeOC6H4
p-FC6H4
p-ClC6H4
m-ClC6H4
m-FC6H4
(anti:syn)
1
2
3
4
5
6
7
8
9
5.5
5.5
6.5
12
5.5
5.5
3.5
5
2a , 65 (100:0)
2b, 75 (100:0)
2c, 71 (100:0)
2d , 85 (100:0)
2e, 74 (100:0)
2f, 70 (100:0)
2g, 57 (100:0)
2h , 61 (100:0)
2i, 54 (100:0)
SCHEME 4
1-naphthyl
12
a
Isolated yields. b The molar ratio of sulfonated imine with PVK
is 0.5:1.5.
To confirm the reaction mechanism of the formation
of the double aza-Baylis-Hillman product 2, we con-
ducted the reaction of PVK with the normal aza-Baylis-
Hillman adduct 1e under the same conditions (Scheme
4). To our surprise, only trace 2e and the dimer of PVK
were formed.10 We also confirmed that the PVK dimer
does not react with N-sulfonated imine in the presence
of DABCO (Scheme 4). This is simply due to the fact that
the PVK dimer type enolate (shown in mechanism 2 of
Scheme 1) cannot be formed from DABCO with the PVK
dimer. These results suggest that the double aza-Baylis-
Hillman products 2 are not derived from the first mech-
anism as shown in Scheme 1, and this unexpected highly
stereoselective double aza-Baylis-Hillman reaction can
only proceed via the second mechanism. Namely, a PVK
dimer type enolate was formed during the reaction which
further react with N-sulfonated imine to give exclusively
the double aza-Baylis-Hillman adduct.
According to the generally accepted reaction mecha-
nism for the Baylis-Hillman reaction, addition of the
catalyst to the activated olefin furnishes a zwitterion
species (Figure 2, A or B), which reacts with the elec-
trophiles such as N-sulfonated imine to give another
zwitterion species (Figure 2, C or D).1a Namely, it carries
the Lewis base molecule in the next reactions such as
the aldol condensation or Michael addition reaction.
Moreover, the subsequent elimination (E2 or E1cB) from
the betain intermediate (nitrogen and phosphane betain)
should also have some differences (Figure 2, C and D).
Thus, we believe that triphenylphosphine and DABCO
are different Lewis bases which have certainly different
properties such as nucleophilicity. Thus, different results
could be obtained in the aza-Baylis-Hillman reaction of
N-sulfonated imines with PVK. But it is very difficult to
strictly clarify the differences between phosphine Lewis
bases and nitrogen Lewis bases. On the basis of these
SCHEME 3
(Table 3). The substituents on the benzene ring do not
significantly affect the reaction rate (Table 3).
It should be emphasized here that for other Michael
acceptors such as MVK, methyl acrylate, and acrylonitrile
no such double aza-Baylis-Hillman reaction product can
be observed at all. To expand the scope and explore the
limitations of this interesting aza-Baylis-Hillman reac-
tion, we tried to synthesize aliphatic N-sulfonated imines
as starting materials. However, we found that many of
these are very labile, even stored in a refrigerator under
-20 °C. So far we prepared two aliphatic N-tosylated
imines, 3 and 4, according to the literature9 which must
be used immediately for the reaction. Aliphatic N-
tosylated imine 4 is more stable than aliphatic N-
tosylated imine 3. In the aza-Baylis-Hillman reaction
of 3 with PVK in the presence of PPh3 under the same
conditions as those described above, the corresponding
normal aza-Baylis-Hillman adduct 5 was formed in 15%
yield along with some unidentified products (Scheme 3).
Using DABCO as a Lewis base for this reaction, none of
the corresponding aza-Baylis-Hillman adduct was formed,
but many unidentified products were formed. In the case
of aliphatic N-tosylated imine 4, the reaction gave many
unidentified products using either PPh3 or DABCO as a
promoter (Scheme 3).
(10) In our previous report, we confirmed that, in the Baylis-
Hillman reaction of arylaldehyde (1.0 equiv) with MVK (2.0 equiv) in
the presence of catalytic amounts of DABCO (0.1 equiv) in DMF or
DMSO, the double Baylis-Hillman reaction product was formed via
the first reaction mechanism as shown in Scheme 1 (please see ref 5).
But the stereoselectivities of the corresponding double Baylis-Hillman
reaction adducts are low (∼2:3) along with the normal Baylis-Hillman
reaction product.
(9) The aliphatic N-sulfonated imines
according to the literature: Chemla, F.; Hebbe, V.; Normant, J . F.
Synthesis 2000, 1, 75.
3 and 4 were prepared
4786 J . Org. Chem., Vol. 68, No. 12, 2003

Double Aza-Baylis-Hillman Reaction of Imines with PVK
SCHEME 5
SCHEME 7
SCHEME 6
charge, and (iii) arrangement of the other substituents
on the PVK enolate and N-sulfonated imine to minimize
steric interactions overall. As can be seen from the
Newman projection, path 1 is the favored way for the
formation of 2 to give the anti-product and path 2 is
disfavored because it suffers from severe steric interac-
tion between R and the enolate of the PVK dimer
(Scheme 6).
Furthermore, we also tried to use 4-(3-ethyl-4-oxa-1-
azatricyclo[4.4.0.03,8]dec-5-yl)quinolin-6-ol (TQO) reported
by Hatakeyama as a chiral Lewis base for this reaction
because it is very easily prepared from (+)-quinidine2a
and high enantiomeric excesses have been achieved in
the reactions of 1,1,1,3,3,3-hexafluoroisopropyl acrylate
with arylaldehydes (Scheme 7).2 We found that the
double aza-Baylis-Hillman adduct was also obtained in
very high yield as a sole product with the anti-configu-
ration and 17% ee (column, Chiralcel OD; eluent, 95:5
hexane-2-propanol mixture; flow rate, 1.0 mL min-1
;
detection, 254 nm light). Now we are exploring some
novel chiral Lewis bases to get high ee in this interesting
double aza-Baylis-Hillman reaction.
Con clu sion
We found that, in the aza-Baylis-Hillman reaction of
sulfonated imines with PVK using DABCO as a Lewis
base, double aza-Baylis-Hillman adduct 2 (diadduct) was
exclusively formed in the anti-configuration, which was
confirmed to be derived from the Baylis-Hillman reac-
tion of the enolate of the PVK dimer induced by DABCO
and PVK with N-tosylated imine. Efforts are under way
to elucidate the mechanistic details of this reaction and
to disclose the scope and limitations of this reaction.
Work along this line is currently in progress.
results, at the present stage we can only speculate that
the PVK enolate B derived from triphenylphosphine and
PVK could be easily formed under the same conditions
with higher nucleophilicity and then immediately react
with N-sulfonated imine (1,2-addition) to give the normal
aza-Baylis-Hillman adducts 1 in high yields. For nitro-
gen Lewis base DABCO, the PVK enolate A derived from
DABCO and PVK would have lower nucleophilicity, react
more easily with another PVK to give the enolate E of
the PVK dimer (PVK dimer type enolate) through Michael
addition (1,4-addition) with higher nucleophilicity, and
subsequently react with N-sulfonated imine (1,2-addition)
to exclusively give the corresponding double aza-Baylis-
Hillman adducts 2 in high yields (Scheme 5).
In Scheme 6, we elucidated the open, extended transi-
tion state for the stereoselective formation of 2 on the
basis of the previous investigations.11 This reaction
proceeded in a stepwise manner. It involves (i) a stag-
gered arrangement of bonds around the interacting
sp2-sp2 centers, (ii) an anti relationship of the PVK
enolate and imino group (CdN) to maximize the distance
between the oxygen atom and nitrogen atom, which, in
the transition state, will both have partial negative
Exp er im en ta l Section
Gen er a l Rem a r k s. Unless otherwise stated, all reactions
were carried out under an argon atmosphere. Phenyl vinyl
ketone12 and all N-tosylated imines13 were prepared according
to the literature. Infrared spectra were measured on
a
spectrometer. 1H NMR and 13C NMR spectra were recorded
at 300 and 75 MHz, respectively. Mass spectra were recorded
by the EI method. All solid compounds reported in this paper
gave satisfactory CHN microanalyses. Melting points are
uncorrected.
Typ ica l Rea ction P r oced u r e for th e Tr ip h en ylp h os-
p h in e-Ca ta lyzed Aza -Ba ylis-Hillm a n Rea ction of P h en -
yl Vin yl Keton e w ith N-Ben zylid en e-4-m eth ylben zen e-
su lfon a m id e.
(11) (a) Nelson, S. G. Tetrahedron: Asymmetry 1998, 9, 357. (b)
Atkinson, R. S., Ed. Stereoselective Synthesis; J ohn Wiley & Sons: New
York, pp 218-242.
(12) Burckhalter, J . H.; Fuson, R. C. J . Am. Chem. Soc. 1948, 70,
4184.
(13) Love, B. E.; Raje, P. S. Synlett 1994, 493.
J . Org. Chem, Vol. 68, No. 12, 2003 4787

Shi and Xu
To a solution of N-benzylidene-4-methylbenzenesulfonamide
(129 mg, 0.5 mmol) and triphenylphosphine (13 mg, 0.05
mmol) in THF (1.0 mL) at room temperature was added phenyl
vinyl ketone (99 mg, 0.75 mmol). The reaction was monitored
by TLC; when the imine disappeared, the solvent was removed
under reduced pressure, and the residue was purified by flash
chromatography [SiO2, EtOAc-petroleum ether (1:5)] to yield
1a (180 mg, 92%) as a colorless solid.
472 (M+ + 2, 0.59), 316 (M+ - 156, 100), 316 (M+ - 154, 97.39).
Anal. Calcd for 4C23H20BrNO3S‚C6H6: C, 59.82; H, 4.82; N,
2.85. Found: C, 59.75; H, 4.86; N, 2.77.
Da ta for N-[2-ben zoyl-1-(2,3-d ich lor op h en yl)a llyl]-4-
m eth ylben zen esu lfon a m id e (1f): colorless solid (199 mg,
87%); mp 165-166 °C; IR (CHCl3) ν 1655 cm-1 (CdO); 1H NMR
(CDCl3, TMS, 300 MHz) δ 2.37 (3H, s, Me), 5.75 (1H, s), 5.80
(1H, d, J ) 8.8 Hz), 6.04 (1H, s), 6.31 (1H, d, J ) 8.8 Hz), 7.08
(1H, dd, J ) 8.2, 7.8 Hz, Ar), 7.19 (2H, d, J ) 8.1 Hz, Ar),
7.31-7.32 (1H, m, Ar), 7.36-7.41 (3H, m, Ar), 7.51-7.60 (3H,
m, Ar), 7.68 (2H, d, J ) 8.1 Hz, Ar); 13C NMR (CDCl3, TMS,
75.44 MHz) δ 20.83, 56.91, 105.52, 126.52, 126.54, 126.72,
127.04, 127.71, 128.79, 128.92, 129.12, 130.25, 132.41, 132.71,
136.09, 137.48, 142.85, 142.99, 196.04; MS (EI) m/e 328 (M+
- 132, 5.16), 304 (M+ - 156, 100). Anal. Calcd for C23H19Cl2-
NO3S: C, 60.00; H, 4.16; N, 3.04. Found: C, 60.22; H, 4.01;
N, 3.03.
Da t a for N-(2-b en zoyl-1-p h en yla llyl)-4-m et h ylb en -
zen esu lfon a m id e (1a ): colorless solid; mp 141-143 °C; IR
(CHCl3) ν 1650 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz)
δ 2.40 (3H, s, Me), 5.46 (1H, d, J ) 8.4 Hz), 5.76 (1H, s), 5.91
(1H, d, J ) 8.4 Hz), 6.13 (1H, s), 7.19-7.25 (7H, m, Ar), 7.36-
7.42 (2H, m, Ar), 7.50-7.56 (3H, m, Ar), 7.72 (2H, d, J ) 8.7
Hz, Ar); 13C NMR (CDCl3, TMS, 75.44 MHz) δ 21.48, 59.72,
126.54, 127.23, 127.77, 128.23, 128.66, 128.87, 129.41, 129.54,
132.69, 137.05, 137.52, 138.67, 143.35, 145.23, 196.90; MS (EI)
m/e 260 (M+ - 131, 5.94), 236 (M+ - 155, 100). Anal. Calcd for
Da ta for N-[2-ben zoyl-1-(4-m eth ylp h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1g): colorless solid (171 mg, 84%);
mp 111-112 °C; IR (CHCl3) ν 1654 cm-1 (CdO); 1H NMR
(CDCl3, TMS, 300 MHz) δ 2.26 (3H, s, Me), 2.39 (3H, s, Me),
5.41 (1H, d, J ) 8.1 Hz), 5.74 (1H, s), 5.81 (1H, d, J ) 8.6 Hz),
6.13 (1H, s), 7.02 (2H, d, J ) 8.1 Hz, Ar), 7.08 (2H, d, J ) 8.1
Hz), 7.22 (2H, d, J ) 8.4 Hz, Ar), 7.35-7.40 (2H, m), 7.49-
7.56 (3H, m, Ar), 7.71 (2H, d, J ) 8.4 Hz, Ar); 13C NMR (CDCl3,
TMS, 75.44 MHz) δ 21.24, 21.75, 59.45, 126.79, 127.49, 128.42,
128.45, 128.71, 129.57, 129.69, 129.75, 132.88, 135.94, 137.32,
137.73, 143.53, 145.76, 197.07; MS (EI) m/e 274 (M+ - 132,
5.90), 250 (M+ - 156, 100.00). Anal. Calcd for C24H23NO3S:
C, 71.08; H, 5.72; N, 3.45. Found: C, 71.12; H, 5.56; N, 3.32.
Da ta for N-[2-ben zoyl-1-(3-m eth ylp h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1h ): colorless solid (202 mg,
C
23H21NO3S: C, 70.56; H, 5.41; N, 3.58. Found: C, 70.41; H,
5.58; N, 3.49.
Da ta for N-[2-ben zoyl-1-(4-m eth oxyp h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1b): colorless solid (158 mg, 75%);
mp 91-92 °C; IR (CHCl3) ν 1655 cm-1 (CdO); 1H NMR (CDCl3,
TMS, 300 MHz) δ 2.39 (3H, s, Me), 3.73 (3H, s, OMe), 5.40
(1H, d, J ) 8.2 Hz), 5.72 (1H, s), 5.81 (1H, d, J ) 8.2 Hz), 6.11
(1H, s), 6.74 (2H, d, J ) 8.4 Hz), 7.10 (2H, d, J ) 8.4 Hz, Ar),
7.22 (2H, d, J ) 7.9 Hz, Ar), 7.35-7.42 (2H, m, Ar), 7.50-7.58
(3H, m, Ar), 7.70 (2H, d, J ) 7.9 Hz, Ar); 13C NMR (CDCl3,
TMS, 75.44 MHz) δ 21.43, 55.15, 58.92, 113.97, 127.20, 127.88,
128.01, 128.17, 129.39, 129.46, 130.75, 132.59, 137.06, 137.50,
143.23, 145.66, 159.02, 196.81; MS (EI) m/e 290 (M+ - 131,
5.42), 266 (M+ - 155, 100). Anal. Calcd for C24H23NO4S: C,
68.39; H, 5.50; N, 3.32. Found: C, 68.44; H, 5.63; N, 3.09.
1
99.5%); mp 144-146 °C; IR (CHCl3) ν 1653 cm-1 (CdO); H
NMR (CDCl3, TMS, 300 MHz) δ 2.29 (3H, s, Me), 2.46 (3H, s,
Me), 5.49 (1H, d, J ) 8.4 Hz), 5.81 (1H, s), 5.91 (1H, d, J ) 8.4
Hz), 6.20 (1H, s), 7.05 (2H, d, J ) 7.5 Hz, Ar), 7.06 (1H, s),
7.29 (2H, d, J ) 8.7 Hz, Ar), 7.42-7.47 (2H, m, Ar), 7.50-7.55
(3H, m, Ar), 7.77 (2H, d, J ) 8.7 Hz, Ar); 13C NMR (CDCl3,
TMS, 75.44 MHz) δ 21.57, 21.73, 59.55, 123.83, 127.51, 127.79,
128.47, 128.73, 129.70, 129.73, 132.91, 137.33, 137.77, 138.51,
138.78, 143.53, 145.77, 197.02; MS (EI) m/e 274 (M+ - 132,
4.42), 250 (M+ - 156, 100). Anal. Calcd for C24H23NO3S: C,
71.08; H, 5.72; N, 3.45. Found: C, 71.22; H, 5.57; N, 3.28.
Da ta for N-[2-ben zoyl-1-(4-eth ylp h en yl)a llyl]-4-m eth -
ylben zen esu lfon a m id e (1i): colorless solid (143 mg, 68%);
mp 102-104 °C; IR (CHCl3) ν 1654 cm-1 (CdO); 1H NMR
(CDCl3, TMS, 300 MHz) δ 1.17 (3H, t, J ) 7.8 Hz, Me), 2.40
(3H, s, Me), 2.56 (2H, q, J ) 7.8 Hz, CH2), 5.44 (1H, d, J ) 8.2
Hz), 5.76 (1H, s), 5.84 (1H, d, J ) 8.2 Hz), 6.14 (1H, s), 7.05
(2H, d, J ) 7.8 Hz, Ar), 7.11 (2H, d, J ) 8.8 Hz, Ar), 7.23 (2H,
d, J ) 8.2 Hz, Ar), 7.36-7.41 (2H, m, Ar), 7.50-7.57 (3H, m,
Ar), 7.71 (2H, d, J ) 8.2 Hz, Ar); 13C NMR (CDCl3, TMS, 75.44
MHz) δ 15.36, 21.46, 28.33, 59.24, 126.59, 127.22, 128.09,
128.16, 128.48, 129.42, 129.45, 132.58, 135.86, 137.09, 137.49,
143.19, 143.76, 145.51, 196.80; MS (EI) m/e 288 (M+ - 132,
5.97), 264 (M+ - 156, 100). Anal. Calcd for C25H25NO3S: C,
71.57; H, 6.01; N, 3.34. Found: C, 71.87; H, 6.17; N, 3.21.
Typ ica l Rea ction P r oced u r e for th e DABCO-Ca ta -
lyzed a za -Ba ylis-Hillm a n Rea ction of P h en yl Vin yl
Keton e w ith N-Ben zylid en e-4-m eth ylben zen esu lfon a -
m id e.
Da ta for N-[2-ben zoyl-1-(4-flu or op h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1c): colorless solid (189 mg, 93%);
mp 138-140 °C; IR (CHCl3) ν 1654 cm-1 (CdO); 1H NMR
(CDCl3, TMS, 300 MHz) δ 2.39 (3H, s, Me), 5.43 (1H, d, J )
8.5 Hz), 5.74 (1H, s), 6.01 (1H, d, J ) 8.5 Hz), 6.08 (1H, s),
6.89-6.95 (2H, dd, J ) 8.6 Hz, 8.6 Hz), 7.18-7.22 (2H, m, Ar),
7.24 (2H, d, J ) 8.2 Hz, Ar), 7.37-7.42 (2H, m, Ar), 7.52-7.56
(3H, m, Ar), 7.70 (2H, d, J ) 8.2 Hz, Ar); 13C NMR (CDCl3,
TMS, 75.44 MHz) δ 21.41, 58.81, 115.40 (d, J C-F ) 21.35 Hz),
115.55, 127.12, 128.22, 128.33, 128.44, 128.63, 129.43 (d, J C-F
) 10.94 Hz), 132.76, 134.53 (d, J C-F ) 3.47 Hz), 136.82, 137.41,
143.40, 145.20, 167.07 (d, J C-F ) 246.46 Hz), 196.67; MS (EI)
m/e 278 (M+ - 132, 4.68), 254 (M+ - 155, 100). Anal. Calcd.
for C23H20FNO3S: C, 67.46; H, 4.92; N, 3.42. Found: C, 67.75;
H, 5.16; N, 3.32.
Da ta for N-[2-ben zoyl-1-(4-ch lor op h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1d ): colorless solid (190 mg,
1
89.2%); mp 119-121 °C; IR (CHCl3) ν 1654 cm-1 (CdO); H
NMR (CDCl3, TMS, 300 MHz) δ 2.39 (3H, s, Me), 5.41 (1H, d,
J ) 8.5 Hz), 5.74 (1H, s), 6.03 (1H, d, J ) 8.5 Hz), 6.07 (1H,
s), 7.14-7.20 (5H, m, Ar), 7.21 (2H, d, J ) 8.1 Hz, Ar), 7.35-
7.40 (2H, m, Ar), 7.50-7.55 (3H, m, Ar), 7.68 (2H, d, J ) 8.1
Hz, Ar); 13C NMR (CDCl3, TMS, 75.44 MHz) δ 21.51, 59.29,
127.19, 128.00, 128.33, 128.77, 129.25, 129.42, 129.60, 132.90,
133.65, 136.84, 137.31, 137.49, 143.53, 144.85, 196.79; MS (EI)
m/e 294 (M+ - 132, 3.72), 270 (M+ - 155, 100). Anal. Calcd
for C23H20ClNO3S: C, 70.56; H, 5.41; N, 3.58. Found: C, 70.41;
H, 5.58; N, 3.49.
To a solution of N-benzylidene-4-methylbenzenesulfonamide
(65 mg, 0.25 mmol) and DABCO (3 mg, 0.025 mmol) in THF
(0.5 mL) at room temperature was added phenyl vinyl ketone
(99 mg, 0.75 mmol). After the resulting solution was stirred
for 5.5 h at room temperature, the solvent was removed under
reduced pressure, and the residue was purified by flash
chromatography [SiO2, EtOAc-petroleum ether (1:5)] to yield
2a (85 mg, 65%) as a colorless solid.
Da ta for N-[2-ben zoyl-1-(4-br om op h en yl)a llyl]-4-m e-
th ylben zen esu lfon a m id e (1e): colorless solid (197 mg, 84%);
mp 114-115 °C; IR (CHCl3) ν 1654 cm-1 (CdO); 1H NMR
(CDCl3, TMS, 300 MHz) δ 2.39 (3H, s, Me), 5.39 (1H, d, J )
8.6 Hz), 5.74 (1H, s), 6.03 (1H, d, J ) 8.6 Hz), 6.07 (1H, s),
7.10 (2H, d, J ) 8.6 Hz, Ar), 7.21 (2H, d, J ) 8.3 Hz, Ar), 7.34
(2H, d, J ) 8.6 Hz, Ar), 7.39 (2H, d, J ) 7.1 Hz, Ar), 7.50-
7.55 (3H, m, Ar), 7.68 (2H, d, J ) 8.3 Hz, Ar); 13C NMR (CDCl3,
TMS, 75.44 MHz) δ 21.41, 59.10, 121.68, 127.08, 128.22,
128.30, 128.32, 129.02, 129.32, 129.49, 131.60, 132.78, 136.74,
137.76, 143.42, 144.81, 196.58; MS (EI) m/e 470 (M+, 0.62),
Da ta for N-(2,4-d iben zoyl-1-p h en ylp en t-4-en yl)-4-m e-
th ylben zen esu lfon a m id e (2a ): colorless solid; mp 112-113
°C; IR (CHCl3) ν 1651 cm-1 (CdO), 1666 cm-1 (CdO); 1H NMR
4788 J . Org. Chem., Vol. 68, No. 12, 2003

Double Aza-Baylis-Hillman Reaction of Imines with PVK
(CDCl3, TMS, 300 MHz) δ 2.29 (3H, s, Me), 2.94 (1H, dd, J )
13.2, 9.0 Hz), 3.02 (1H, dd, J ) 13.2, 6.6 Hz), 4.24 (1H, ddd, J
) 9.0, 6.6, 4.2 Hz), 4.86 (1H, dd, J ) 9.6, 4.2 Hz), 5.87 (1H, s),
6.24 (1H, s), 6.85-6.95 (6H, m), 7.00 (2H, d, J ) 8.3 Hz), 7.32
(2H, d, J ) 7.5 Hz), 7.41-7.49 (5H, m, Ar), 7.53-7.59 (1H,
m), 7.66 (2H, d, J ) 7.9 Hz, Ar), 7.73 (2H, d, J ) 8.1 Hz, Ar);
13C NMR (CDCl3, TMS, 75 MHz) δ 21.28, 34.43, 49.02, 58.48,
126.44, 126.75, 126.92, 128.04, 128.28, 128.32, 128.38, 128.56,
128.97, 129.34, 132.33, 132.68, 133.59, 136.59, 137.53, 138.15,
138.77, 142.58, 198.04, 204.18; MS (EI) m/e 368 (M+ - 154,
29.15), 105 (PhCO+, 100.00). Anal. Calcd for C32H29NO4S: C,
73.40; H, 5.58; N, 2.67. Found: C, 73.54; H, 5.65; N, 2.51.
(2H, d, J ) 6.9 Hz, Ar), 7.76 (2H, d, J ) 8.1 Hz, Ar); 13C NMR
(CDCl3, TMS, 75 MHz) δ 21.31, 34.46, 48.98, 57.76, 114.89 (d,
J C-F ) 21.75 Hz), 126.74, 128.16 (d, J C-F ) 4.16 Hz), 128.33,
128.39, 128.67, 129.04, 129.35, 132.42, 132.91, 133.81, 134.67
(d, J C-F ) 2.4 Hz), 136.35, 137.48, 138.12, 142.33, 142.87,
161.58 (d, J C-F ) 246.09 Hz), 198.09, 204.11; MS (EI) m/e 386
(M+ - 155, 30.12), 105 (PhCO+, 100.00). Anal. Calcd for C32H28
-
FNO4S: C, 70.96; H, 5.21; N, 2.59. Found: C, 70.98; H, 5.26;
N, 2.67.
Da ta for N-[2,4-d iben zoyl-1-(4-ch lor op h en yl)p en t-4-
en yl]-4-m eth ylben zen esu lfon a m id e (2f): colorless solid (98
mg, 70%); mp 137-138 °C; IR (CHCl3) ν 1650 cm-1 (CdO),
1666 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ 2.35
(3H, s, Me), 2.94 (1H, dd, J ) 13.5, 9.0 Hz), 3.03 (1H, dd, J )
13.5, 6.0 Hz), 4.25 (1H, ddd, J ) 9.0, 6.0, 3.9 Hz), 4.84 (1H,
dd, J ) 9.3, 3.9 Hz), 5.91 (1H, s), 6.27 (1H, s), 6.81 (2H, d, J
) 8.4 Hz), 6.90 (2H, d, J ) 9.3 Hz), 7.05 (2H, d, J ) 7.8 Hz),
7.33-7.38 (2H, m), 7.44-7.52 (5H, m, Ar), 7.56-7.62 (1H, m),
7.69 (2H, d, J ) 6.9 Hz, Ar), 7.79 (2H, d, J ) 7.2 Hz, Ar); 13C
NMR (CDCl3, TMS, 75 MHz) δ 21.34, 34.47, 48.84, 57.91,
126.78, 128.05, 128.18, 128.35, 128.45, 128.73, 129.11, 129.38,
132.46, 132.83, 132.94, 133.88, 136.33, 137.38, 137.47, 138.01,
142.32, 143.01, 198.08, 203.86; MS (EI) m/e 402 (M+ - 156,
19.18), 105 (PhCO+, 100.00). Anal. Calcd for C32H28ClNO4S:
C, 68.87; H, 5.06; N, 2.51. Found: C, 69.04; H, 5.07; N, 2.35.
Da ta for N-[2,4-d iben zoyl-1-(3-m eth ylp h en yl)p en t-4-
en yl]-4-m eth ylben zen esu lfon a m id e (2b): colorless solid
(101 mg, 75%); mp 130-132 °C; IR (CHCl3) ν 1651 cm-1
(CdO), 1667 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ
1.98 (3H,s), 2.30 (3H, s, Me), 2.95 (1H, dd, J ) 13.2, 8.7 Hz),
3.03 (1H, dd, J ) 13.2, 6.3 Hz), 4.24 (1H, ddd, J ) 8.7, 6.3, 3.9
Hz), 4.83 (1H, dd, J ) 9.3, 3.9 Hz), 5.88 (1H, s), 6.27 (1H, s),
6.55 (1H, s), 6.67-6.87 (4H, m), 7.02 (2H, d, J ) 8.7 Hz), 7.27-
7.34 (2H, m), 7.42-7.49 (5H, m, Ar), 7.54-7.60 (1H, m), 7.68
(2H, d, J ) 7.2 Hz, Ar), 7.75 (2H, d, J ) 7.2 Hz, Ar); 13C NMR
(CDCl3, TMS, 75 MHz) δ 20.91, 21.22, 48.94, 58.42, 123.63,
126.68, 127.12, 127.59, 127.93, 128.23, 128.34, 128.49, 128.81,
129.30, 132.28, 132.70, 133.51, 136.58, 137.46, 137.50, 138.13,
138.35, 142.42, 142.54, 198.01, 204.14; MS (EI) m/e 382 (M+
Da ta for N-[2,4-d iben zoyl-1-(3-ch lor op h en yl)p en t-4-
en yl]-4-m eth ylben zen esu lfon a m id e (2g): colorless solid (80
mg, 57%); mp 165-167 °C; IR (CHCl3) ν 1650 cm-1 (CdO),
1668 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ 2.30
(3H, s, Me), 2.93 (1H, dd, J ) 13.5, 9.0 Hz), 3.04 (1H, dd, J )
13.5, 6.0 Hz), 4.24 (1H, ddd, J ) 9.0, 6.0, 3.9 Hz), 4.81 (1H,
dd, J ) 9.6, 3.9 Hz), 5.91 (1H, s), 6.30 (1H, s), 6.70-6.78 (2H,
m), 6.85-6.89 (3H, m), 7.02 (2H, d, J ) 8.4 Hz), 7.31-7.36
(2H, m), 7.43-7.50 (5H, m, Ar), 7.55-7.60 (1H, m), 7.68 (2H,
d, J ) 7.8 Hz, Ar), 7.78 (2H, d, J ) 7.2 Hz, Ar); 13C NMR
(CDCl3, TMS, 75 MHz) δ 21.14, 34.22, 48.66, 57.73, 124.66,
126.45, 126.63, 126.93, 128.16, 128.27, 128.49, 128.94, 129.18,
129.22, 132.26, 132.86, 133.64, 133.78, 136.08, 137.27, 137.65,
140.48, 142.04, 142.82, 197.89, 203.51; MS (EI) m/e 402 (M+
- 155, 41.88), 105 (PhCO+, 100.00). Anal. Calcd for C33H31
-
NO4S: C, 73.72; H, 5.81; N, 2.61. Found: C, 73.78; H, 5.73;
N, 2.35.
Da ta for N-[2,4-d iben zoyl-1-(4-m eth ylp h en yl)p en t-4-
en yl]-4-m eth ylben zen esu lfon a m id e (2c): colorless solid
(95 mg, 71%); mp 118-119 °C; IR (CHCl3) ν 1652 cm-1
(CdO), 1669 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ
2.12 (3H, s), 2.29 (3H, s, Me), 2.95 (1H, dd, J ) 13.5, 9.0 Hz),
3.03 (1H, dd, J ) 13.5, 6.6 Hz), 4.23 (1H, ddd, J ) 9.0, 6.6, 3.6
Hz), 4.81 (1H, dd, J ) 9.3, 3.6 Hz), 5.84 (1H, s), 6.21 (1H, s),
6.73 (5H, s), 6.78 (2H, d, J ) 9.3 Hz, NH), 6.99 (2H, d, J ) 8.1
Hz), 7.28-7.33 (2H, m), 7.39-7.47 (5H, m, Ar), 7.52-7.57 (1H,
m), 7.63 (2H, d, J ) 7.0 Hz, Ar), 7.74 (2H, d, J ) 8.2 Hz, Ar);
13C NMR (CDCl3, TMS, 75 MHz) δ 20.82, 21.34, 34.41, 49.07,
58.39, 126.44, 126.83, 128.31, 128.47, 128.61, 128.71, 128.83,
128.96, 129.37, 132.34, 132.66, 133.59, 135.77, 136.61, 137.57,
138.21, 142.53, 142.70, 198.05, 204.13; MS (EI) m/e 382 (M+
- 156, 45.04), 105 (PhCO+, 100.00). Anal. Calcd for C32H28
-
ClNO4S: C, 68.87; H, 5.06; N, 2.51. Found: C, 68.84; H, 4.96;
N, 2.28.
Da t a for N-[2,4-d ib en zoyl-1-(3-flu or op h en yl)p en t -4-
en yl]-4-m eth ylben zen esu lfon a m id e (2h ): colorless solid (83
mg, 61%); mp 109-110 °C; IR (CHCl3) ν 1654 cm-1 (CdO),
1680 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ 2.33
(3H, s, Me), 2.96 (1H, dd, J ) 13.5, 9.0 Hz), 3.06 (1H, dd, J )
13.5, 6.3 Hz), 4.28 (1H, ddd, J ) 9.0, 6.3, 3.6 Hz), 4.87 (1H,
dd, J ) 9.6, 3.6 Hz), 5.93 (1H, s), 6.30 (1H, s), 6.53 (2H, d, J
) 9.6 Hz), 6.3-6.71 (2H, m), 6.92-6.98 (2H, m), 7.06 (2H, d,
J ) 7.8 Hz), 7.33-7.38 (2H, m), 7.46-7.53 (5H, m, Ar), 7.58-
7.63 (1H, m), 7.71 (2H, d, J ) 6.9 Hz, Ar), 7.80 (2H, d, J ) 7.2
Hz, Ar); 13C NMR (CDCl3, TMS, 75 MHz) δ 21.29, 34.41, 48.78,
57.88, 113.60 (d, J C-F ) 21.83 Hz), 113.89 (d, J C-F ) 20.70
Hz), 122.23 (d, J C-F ) 2.93 Hz), 126.69, 128.38 (d, J C-F ) 6.23
Hz), 128.67, 129.07, 129.36, 129.60, 129.71, 132.44, 133.03,
133.82, 136.27, 137.46, 138.01, 141.47 (d, J C-F ) 6.15 Hz),
142.24, 142.91, 162.29 (d, J C-F ) 245.70 Hz), 198.09, 203.86;
MS (EI) m/e 386 (M+ - 155, 42.45), 105 (PhCO+, 100.00). Anal.
Calcd for C32H28FNO4S: C, 70.96; H, 5.21; N, 2.59. Found: C,
70.95; H, 5.17; N, 2.39.
Da t a for N-(2,4-d ib en zoyl-1-n a p h t h a len -1-ylp en t -4-
en yl)-4-m eth ylben zen esu lfon a m id e (2i): colorless solid (78
mg, 54%); mp 164-165 °C; IR (CHCl3) ν 1651 cm-1 (CdO),
1667 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ 2.22
(3H, s, Me), 3.11 (2H, d, J ) 7.2 Hz), 4.47 (1H, dt, J ) 7.2, 3.3
Hz), 5.76 (1H, dd, J ) 9.3, 3.3 Hz), 6.01 (1H, s), 6.41 (1H, s),
6.82-6.91 (4H, m), 7.06 (1H, d, J ) 9.3 Hz), 7.13-7.18 (2H,
m), 7.32-7.56 (11H, m, Ar), 7.69-7.75 (3H, m), 7.82 (2H, d, J
) 8.4 Hz, Ar); 13C NMR (CDCl3, TMS, 75 MHz) δ 21.20, 34.53,
46.93, 53.91, 121.50, 124.59, 124.65, 125.36, 126.46, 126.58,
127.33, 128.16, 128.31, 128.39, 128.59, 128.81, 128.90, 129.36,
- 155, 24.79), 105 (PhCO+, 91.37). Anal. Calcd for C33H31
-
NO4S: C, 73.72; H, 5.81; N, 2.61. Found: C, 73.79; H, 5.73;
N, 2.43.
Da ta for N-[2,4-Diben zoyl-1-(4-m eth oxyp h en yl)p en t-
4-en yl]-4-m eth ylben zen esu lfon a m id e (2d ): colorless solid
(117 mg, 85%); mp 127-128 °C; IR (CHCl3) ν 1651 cm-1
(CdO), 1664 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ
2.31 (3H, s, Me), 2.95 (1H, dd, J ) 13.2, 8.5 Hz), 3.03 (1H, dd,
J ) 13.2, 6.5 Hz), 3.64 (3H, s, Me), 4.23 (1H, ddd, J ) 8.5, 6.5,
3.8 Hz), 4.82 (1H, dd, J ) 8.9, 3.8 Hz), 5.86 (1H, s), 6.23 (1H,
s), 6.47 (1H, d, J ) 8.8 Hz), 6.78 (2H, d, J ) 8.9 Hz), 7.03 (2H,
d, J ) 8.4 Hz), 7.30-7.35 (2H, m), 7.41-7.50 (5H, m, Ar), 7.54-
7.59 (1H, m), 7.65 (2H, d, J ) 6.9 Hz, Ar), 7.76 (2H, d, J ) 6.6
Hz, Ar); 13C NMR (CDCl3, TMS, 75 MHz) δ 21.25, 34.36, 49.07,
54.99, 58.05, 113.35, 126.74, 127.62, 128.21, 128.35, 128.54,
128.90, 129.27, 130.87, 132.26, 132.48, 133.54, 136.58, 137.46,
138.17, 142.40, 142.60, 158.38, 197.94, 204.24; MS (EI) m/e
399 (M+ - 155, 3.79), 105 (PhCO+, 91.37). Anal. Calcd for
C
33H31NO5S: C, 71.59; H, 5.64; N, 2.53. Found: C, 71.51; H,
5.72; N, 2.59.
Da t a for N-[2,4-d ib en zoyl-1-(4-flu or op h en yl)p en t -4-
en yl]-4-m eth ylben zen esu lfon a m id e (2e): colorless solid
(100 mg, 74%); mp 141-142 °C; IR (CHCl3) ν 1650 cm-1
(CdO), 1666 cm-1 (CdO); 1H NMR (CDCl3, TMS, 300 MHz) δ
2.33 (3H, s, Me), 2.94 (1H, dd, J ) 12.6, 9.0 Hz), 3.03 (1H, dd,
J ) 12.6, 6.6 Hz), 4.25 (1H, ddd, J ) 9.0, 6.6, 3.9 Hz), 4.85
(1H, dd, J ) 9.6, 3.9 Hz), 5.89 (1H, s), 6.26 (1H, s), 6.59-6.65
(2H, m), 6.82-6.90 (3H, m), 7.04 (2H, d, J ) 8.1 Hz), 7.31-
7.36 (2H, m), 7.43-7.51 (5H, m, Ar), 7.55-7.60 (1H, m), 7.66
J . Org. Chem, Vol. 68, No. 12, 2003 4789

Shi and Xu
129.71, 132.30, 133.34, 133.46, 133.51, 136.44, 137.42, 138.01,
142.41, 142.52, 197.76, 204.31; MS (EI) m/e 418 (M+ - 156,
16.95), 105 (PhCO+, 100.00). Anal. Calcd for C36H31NO4S: C,
75.37; H, 5.45; N, 2.44. Found: C, 75.39; H, 5.21; N, 2.19.
Da t a for N-[1-(1-b en zoylvin yl)p en t yl]-4-m et h ylb en -
zen esu lfon a m id e (5): viscous liquid; IR (CHCl3) ν 1685 cm-1
40.38), 216 (M+ - 155, 32.68); HRMS m/e calcd for C17H16
-
NO3S 314.08509, found 314.08501.
Ack n ow led gm en t. We thank the State Key Project
of Basic Research (Project 973) (Grant No. G2000048007),
Shanghai Municipal Committee of Science and Technol-
ogy, and National Natural Science Foundation of China
for financial support (Grants Nos. 20025206 and
20272069).
1
(CdO); H NMR (CDCl3, TMS, 300 MHz) δ 0.84 (3H, J ) 7.5
Hz, Me), 1.20-1.35 (4H, m, CH2CH2), 1.58-1.75 (2H, m, CH2),
2.38 (3H, s, Me), 4.13 (1H, dt, J ) 9.3, 7.8 Hz, CH), 5.52 (1H,
s, dCH), 5.62 (1H, d, J ) 9.3 Hz, NH), 5.81 (1H, s, dCH), 7.22
(2H, d, J ) 8.1 Hz, Ar), 7.37-7.43 (2H, m, Ar), 7.49-7.58 (3H,
m, Ar), 7.71 (2H, d, J ) 8.1 Hz, Ar); 13C NMR (CDCl3, TMS,
75 MHz) δ 13.87, 21.44, 22.05, 28.31, 35.15, 57.67, 127.15,
128.16, 129.09, 129.37, 129.45, 132.57, 137.30, 138.03, 143.06,
145.39, 197.63; MS (EI) m/e 372 (M+ + 1, 6.70), 314 (M+ - 57,
Su p p or tin g In for m a tion Ava ila ble: X-ray crystal data
of 2a . This material is available free of charge via the Internet
at http://pubs.acs.org.
J O034114F
4790 J . Org. Chem., Vol. 68, No. 12, 2003