Construction of 3-allylidene-4-vinyltetrahydrofurans and 3-allylidene-4-vinylpyrrolidines via sequential domino allylation/olefination of C-C triple bonds

Article abstract of DOI:10.1016/j.tet.2011.09.026

An efficient method via sequential domino allylation/olefination of C-C triple bonds for the syntheses of five-membered heterocycles was developed by treatment 1,6-enynes with alkenes in the presence of a palladium catalyst. The configurations of the 1,3-

Full text of DOI:10.1016/j.tet.2011.09.026

Tetrahedron 67 (2011) 8710e8716
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Construction of 3-allylidene-4-vinyltetrahydrofurans and 3-allylidene-4-
vinylpyrrolidines via sequential domino allylation/olefination of CeC triple bonds
,
a
a
a,b,
Tuan-jie Meng a, Yimin Hu a , Quansheng Zhao , Tao Yu , Shaowu Wang
*
*
a Laboratory of Functionalized Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu, Anhui 241000, PR China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 July 2011
Received in revised form 6 September 2011
Accepted 9 September 2011
Available online 14 September 2011
An efficient method via sequential domino allylation/olefination of CeC triple bonds for the syntheses of
five-membered heterocycles was developed by treatment 1,6-enynes with alkenes in the presence
of a palladium catalyst. The configurations of the 1,3-dienes of the five-membered heterocycles are
stereocontrolled.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Enynes
Domino reaction
Cyclization
Catalysis
Palladium
1. Introduction
bonds has been less studied. Conceptually, the installation of
the electron-withdrawing functionality by means of an organo-
One of the challenges of using organometallic chemistry is
finding reactions and strategies that allow for the facile conversion
of simple compounds into complex materials, medicines, or mol-
ecules of theoretical interest.1 Palladium-catalyzed cyclization
is an important method for the construction of ring systems
because it offers an efficient entryway to cyclic compounds from
readily available acyclic substrates.2 Cyclization reactions of 1,6-
enynes have been widely investigated with various palladium
catalysts.3 Most cyclization reactions of 1,6-enynes are initiated by
hydropalladation,4 carbopalladation,5 acetoxypalladation,6 hal-
opalladation7 or metalpalladation8 of the triple bond to provide
a vinylpalladium intermediate. Intramolecular carbopalladation of
the double bond realizes the cyclization of 1,6-enynes (Eq. 1). The
cyclization process involving alkenyl-,9 or arylpalladium10,11 halide
complexes, which were generated via oxidative addition of alkenyl
or aryl halides undergoing cyclic carbopalladation of alkynes
affording vinylpalladium species, has also been widely studied
(Eq. 2). The intramolecular insertion of the triple bond to the
metallic elementary step, such as the insertion of an alkyne into
a vinylepalladium bond12 followed by a tandem process is required
in the isomerization process. This step is more than a methodo-
logical extension of the Heck reaction as it could also provide access
to heterodomino reactions.13 We describe herein a new method
via sequential domino allylation/olefination of CeC triple bonds
for the syntheses of 3-allylidene-4-vinyltetrahydrofurans and
3-allylidene-4-vinylpyrrolidines.
p-allylpalladium species has also been extensively studied (Eq. 3),
but the sequential domino allylation/olefination of CeC triple
* Corresponding authors. Tel.: þ86 553 386 9310; fax: þ86 553 388 3517; e-mail
addresses: yiminhu@mail.ahnu.edu.cn (Y. Hu), swwang@mail.ahnu.edu.cn
(S. Wang).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.09.026

T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
8711
further explore the generality and scope of the allylation/olefination
of CeC triple bonds, a variety of enynes 1bef were investigated, and
the results are summarized inTable 2 (entries 5e23). It was found that
1,6-enynes with oxygen and nitrogen linkages could be used in this
domino allylation/olefination of CeC triple bonds. The linkage atoms
had no obvious effect on the reaction. With respect to the substituents
R1 at the alkynes terminus, substituents R1 on 1,6-enynes not only
could be aryl (phenyl, 4-chlorophenyl, and 4-methoxyphenyl), but
also be butyl. But the reaction of the butyl-substituted 1,6-enyne with
alkenes produced the desired products in relative low yields in
comparison with other 1,6-enynes (Table 2, entries 17e19). In-
terestingly, the configuration of the 1,3-butadiene products 3 is ex-
2. Results and discussion
Our initial attempts were aimed at studying the effect of the
solvent on the allylation/olefination of CeC triple bonds (Table 1). In
the presence of the Pd(OAc)2/PPh3 catalyst (5 mol %) and K2CO3
(2 equiv) as a base, the reaction of enyne (1a,1 mmol) and olefin (2a,
3 mmol) in THF at 80 ꢀC afforded 3aa in 54% yield (Table 1, entry 1).
Screening of various solvents revealed that the solvent played
a significant role in this reaction (Table 1, entries 1e5). Only trace
amount of the desired product 3aa was obtained when acetonitrile
was used as a solvent (entry 3). DCE (1,2-dichloroethane) was found
to be the best of all solvents tested (Table 1, entries 1e5). Further
lowering the catalyst loadings from 5 mol % to 3 mol % resulted in
decreased product yields from 76% to 65% (Table 1, entries 5 and 6).
The effect of temperature on the reaction was studied. No desired
product could be observed when the reaction was performed at
room temperature, but most of the starting materials remained
unchanged (Table 1, entry 7). The reaction proceeded sluggishly at
60 ꢀC and was not completed even after two days (Table 1, entry 8).
Raising the temperature to 100 ꢀC resulted in a decrease of the
product yield to 68% (Table 1, entry 9). An examination of the im-
portance of the bases in this reaction revealed that potassium car-
bonate was significantly better than sodium carbonate and
triethylamine (Table 1, entries 10 and 11). Survey of a number of
other palladium catalysts, such as PdCl2, Pd(PPh3)4, and Pd(PPh3)2Cl2
indicated that these catalysts were all less effective than Pd(OAc)2
with regard to the product yields (Table 1, entries 12e14).
1
clusively in the (E,Z)-form, which was assigned by the H NMR and
NOSEY spectra of products 3dc and 3dd, indicating high regio- and
high stereoselectivity for the construction of 1,3-butadiene fragments.
Table 2
Sequential domino allylation/olefination of CeC triple bondsa
Entry
Enyne
Alkene
Product
Yieldb (%)
1
2
3
4
5
6
7
8
Z¼O, R1¼Ph (1a)
R2¼CO2Me (2a)
3aa
3ab
3ac
3ad
3ba
3bb
3bc
3bd
3ca
3cb
3cc
3cd
3da
3db
3dc
3dd
3ea
3ec
3ed
3fa
76
73
78
52
79
72
82
50
75
69
77
48
77
73
76
50
44
47
32
73
70
72
54
1a
R2¼CO2Et (2b)
1a
1a
R2¼CN (2c)
R2¼Ph (2d)
Table 1
Optimization of sequential domino allylation/olefination of CeC triple bondsa
Z¼O, R1¼4-ClePh (1b)
2a
2b
2c
2d
2a
2b
2c
2d
2a
2b
2c
2d
2a
2c
2d
2a
2b
2c
2d
1b
1b
1b
9
Z¼O, R1¼4-MeOePh (1c)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
1c
1c
1c
Z¼TsN, R1¼Ph (1d)
1d
1d
1d
Entry [Pd](mol %)/L
Base (2 equiv) Solvent
THF
Tb (ꢀC) Yieldc (%)
Z¼TsN, R1¼n-Bu (1e)
1e
1e
1
Pd(OAc)2/PPh3 (5:5) K2CO3
80
80
80
54
18
Trace
38
2
Pd(OAc)2/PPh3 (5:5) K2CO3
DMF
CH3CN
Toluene 80
Z¼BocN, R1¼Ph (1f)
3
4
5
6
7
8
9
10
11
12
13
14
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (3:3) K2CO3
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (5:5) K2CO3
Pd(OAc)2/PPh3 (5:5) Na2CO3
Pd(OAc)2/PPh3 (5:5) Et3N
1f
1f
1f
3fb
3fc
3fd
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
80
80
rt
76
65
0
a
General conditions: enyne (1.0 equiv), alkene (3.0 equiv), Pd(OAc)2 (5 mol %),
PPh3 (5 mol %), K2CO3 (2 equiv), DCE (3 mL), 80 ꢀC (oil bath temperature).
60
100
80
80
80
80
80
23
68
14
Trace
11
b
Isolated yields after flash column chromatography.
[PdCl2]/PPh3(5:5)
Pd(PPh3)4(5)
K2CO3
K2CO3
K2CO3
On the basis of the results on the above domino allylation/ole-
fination of CeC triple bonds, we introduced a substituting group at
the 5-position of 1,6-enynes to study the relative stereochemistry
of the five-membered heterocycle products. The results are sum-
marized in Table 3. When the linked atom of 1,6-enyne is oxygen,
the major products are in the trans form. However, use of 1,6-enyne
with tosylamide linkage resulted in the production of cis products
as major outcomes.
The stereochemistry of the products (Table 3) was confirmed by
using NOE methods. In typical examples, NOE interactions were
observed between the vinyl and methine protons of products 3gc
and 3gd (Fig. 1), indicating a trans relationship between these
substituents. The cis configuration of 3ic was assigned based on
strong NOE interaction between the methyl and vinyl protons
(Fig. 1), and further confirmed by the X-ray crystal structure anal-
ysis (Fig. 2).14
46
Trace
[Pd(PPh3)2Cl2](5)
a
Reactions were run in the presence of 3 equiv 2a in appropriate solvents
(0.33 M) for 20 h.
b
Oil bath temperature.
Isolated yield.
c
Under the optimized conditions, we extended the domino allyla-
tion/olefination of CeC triple bonds with a range of enynes and
commercially available alkenes (Table 2, entries 1e4). In Table 2,
enyne 1a readily reacted with electron deficient alkenes, such as
methyl acrylate 2a, ethyl acrylate 2b, acrylonitrile 2c, and styrene 2d
to afford the corresponding products 3aaead in moderate to good
yields (Table 2, entries 1e4). Attempted allylation/olefination of CeC
triple bonds of 1a with methyl methacrylate did not produce the
desired product probably due to the steric/electronic effects. To

8712
T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
Table 3
give intermediate 4. The syn carbopalladation affords the vinyl-
palladium intermediate 5. The insertion of alkene 2 to the
vinylepalladium bond led to alkylpalladium intermediate 6, which
Sequential domino reactions of 5-position substituted 1,6-enynes with olefinsa
liberates 3 and HPdBr after classical
b-hydrogen elimination. A
reductive elimination assisted by potassium carbonate regenerates
palladium(0).15
Entry Enyne
Alkene
Product Yieldb [trans/cis]c
1
2
3
4
5
6
7
Z¼O, R¼Me, R1¼Ph (1g) R2¼CO2Me (2a) 3ga
70d
1g
1g
1g
R2¼CO2Et (2b) 3gb
68 (85/15)
R2¼CN (2c)
R2¼Ph (2d)
3gc
3gd
3hc
3ic
73d
41d
Z¼O, R¼Et, R1¼Ph (1h) 2c
65d
Z¼O, R¼Et, R1¼Ph (1i)
2c
68d
1i
2d
3id
45 (30/70)
a
General conditions: enyne (1.0 equiv), alkene (3.0 equiv), Pd(OAc)2 (5 mol %),
PPh3 (5 mol %), K2CO3 (2 equiv), DCE (3 mL), 80 ꢀC (oil bath temperature).
b
Isolated yields after flash column chromatography.
c
The ratio was determined by 1H NMR.
d
Only transor cis products were isolated depending on heteroatomsin 1,6-enynes.
Scheme 1. Proposed mechanism of synthesis of 3.
Fig. 1. NOE interactions were used to confirm the configuration of the products
(see the Supplementary data).
3. Conclusions
In summary, we have developed a sequential domino allylation/
olefination of CeC triple bonds method for the syntheses of
3-allylidene-4-vinyltetrahydrofurans and 3-allylidene-4-vinylpyrro-
lidines system by treatment of easily available 1,6-enynes with
commercially available alkenes in the presence of a palladium
catalyst. Interestingly, the 1,3-diene units could be constructed in
high regio- and stereoselectivity. Studies addressing the synthetic
scope of the domino reaction and the photophysical and pharma-
cological properties of these new allylidene-vinyl(hetero)cyclic
units are currently underway.
4. Experimental
4.1. General experiment
All the catalytic reactions were performed under an argon at-
mosphere using the oven-dried Schlenk flask. The chemicals were
purchased from Alfa Aesar and Acros Chemicals. All solvents and
materials were pre-dried, redistilled or recrystallized before use. 1H
NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on
a Bruker Avance 300 spectrometer with CDCl3 as the solvent.
Chemical shifts are reported in parts per million by assigning TMS
resonance in the 1H NMR spectra as 0.00 ppm and CDCl3 resonance
in the 13C spectra as 77.0 ppm. All coupling constants (J values)
were reported in hertz (Hz). Column chromatography was per-
formed on silica gel 300e400 mesh. Melting points were de-
termined using a Gallenkamp melting point apparatus and are
uncorrected. The FT-IR spectra were recorded from KBr pellets in
the 4000e400 cmꢁ1 ranges on a Nicolet 5DX spectrometer. Mass
spectra were performed on Micromass GCT-MS. X-ray Crystallog-
raphy diffraction data of 3ic was collected at room temperature
Fig. 2. Molecular structure of compound 3ic. Ellipsiods are drawn at 30% probability.
ꢀ
ꢀ
Selected bond lengths (A) and angles ( ) C9eC10 1.521(3), C9eC13 1.510(3), C13eC14
1.286(3), C10eC15 1.338(3), C15eC16 1.451(3), C16eC17 1.328(3), C8eC9eC10 102.2(2),
C10eC9eC13 112.0(2), C11eC10eC15 122.4(2), C9eC10eC15 127.2(2), C10eC15eC16
121.4(2), C15eC16eC17 125.7(2).
A possible reaction mechanism that accounts for the formation
of products 3 is shown in Scheme 1. Oxidative addition of allyl
bromide to palladium(0) results in the
p-allylpalladium species
that subsequently coordinates with the triple bond of 1,6-enyne to

T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
8713
with a Bruker SMART Apex CCD diffractometer with Mo K
a
radia-
¼0.71073 A) with a graphite monochromator using the
-scan mode. Data reductions and absorption corrections were
nmax 3078, 3028,1633,1597, 1101,1064, 734, 702 cmꢁ1; HRMS: calcd
for C21H21O [MþH]þ 289.1587; found 289.1590.
ꢀ
tion (
l
u
performed with SAINT and SADABS software, respectively. The
structure was solved by direct methods and refined on F2 by full-
matrix least squares using SHELXTL.16 All non-hydrogen atoms
were treated anisotropically. The positions of hydrogen atoms were
generated geometrically. 1,6-Enynes 1aei were prepared by pub-
lished procedures.17
4.2.5. Compound 3ba. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.79
(d, J¼15.6 Hz, 1H; CeCHeCH), 7.35 (d, J¼8.3 Hz, 2H; AreH), 7.03 (m,
J¼8.3 Hz, 2H; AreH), 5.95e5.87 (m, 1H; CHeCHeCH2), 5.35 (d,
J¼15.6 Hz, 1H; CHeCHeCO), 5.29e5.19 (m, 2H; CHeCH2), 4.24 (d,
J¼15.9 Hz, 1H; OeCHHeC), 4.06e4.01 (m, 2H; OeCHHeC,
OeCHHeCH), 3.89e3.81 (m, 2H; OeCHHeCH, CH2eCHeCH), 3.69
(s, 3H; OeCH3); 13C NMR (75 MHz, CDCl3): 167.5, 150.9, 142.8, 137.4,
135.9, 133.7, 130.7, 130.0, 129.1, 119.9, 116.4, 74.2, 71.2, 51.6, 46.7; FT-
IR (neat): nmax 3082, 3028, 1714, 1633, 1288, 1170, 1101, 1062,
839 cmꢁ1; HRMS: calcd for C17H18ClO3 [MþH]þ 305.0939; found
305.0940.
4.2. Synthesis
Enyne 1aei (1.0 equiv), K2CO3 (2.0 equiv), Pd(OAc)2 (5 mol %),
and PPh3 (5 mol %) were added to a degassed solution of alkene
2aed (3.0 equiv) in DCE (3 mL), and the mixture was stirred at
room temperature for half an hour and then heated at 80 ꢀC for
20 h. The reaction mixture was cooled, and then quenched with
water and extracted with EtOAc (3ꢂ5 mL). The combined organic
layers were washed with hydrochloric acid (5%), sodium car-
bonate (5%), and saturated sodium chloride solution. After sepa-
ration, the organic layer was dried over MgSO4 and then
concentrated. The residue was purified by flash chromatography
column (8:1 petroleum ether/EtOAc) to give the corresponding
product 3.
4.2.6. Compound 3bb. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.80
(d, J¼15.6 Hz, 1H; CeCHeCH), 7.35 (d, J¼8.1 Hz, 2H; AreH), 7.03 (m,
J¼8.1 Hz, 2H; AreH), 5.94e5.86 (m, 1H; CHeCHeCH2), 5.34 (d,
J¼15.3 Hz, 1H; CHeCHeCO), 5.29e5.19 (m, 2H; CHeCH2),
4.26e4.01 (m, 5H; OeCH2eC, OeCH2eCH3, OeCHHeCH),
3.89e3.81 (m, 2H; OeCHHeCH, CH2eCHeCH), 1.24 (t, J¼6.6 Hz, 3H;
CH2CH3); 13C NMR (75 MHz, CDCl3): 167.0, 150.7, 142.6, 137.5, 135.9,
133.7, 130.7, 130.0, 129.1, 120.4, 116.4, 74.2, 71.2, 60.4, 46.8, 14.2; FT-
IR (neat): nmax 3082, 3028, 1714, 1633, 1286, 1172, 1101, 1062,
833 cmꢁ1; HRMS: calcd for C18H20ClO3 [MþH]þ 319.1095; found
319.1128.
4.2.1. Compound 3aa. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.82
(d, J¼15.3 Hz, 1H; CeCHeCH), 7.38e7.35 (m, 3H; AreH), 7.10e7.08
(m, 2H; AreH), 5.99e5.90 (m, 1H; CHeCHeCH2), 5.40 (d, J¼15.3 Hz,
1H; CHeCHeCO), 5.31e5.20 (m, 2H; CHeCH2), 4.26 (d, J¼15.3 Hz,
1H; OeCHHeC), 4.08e4.03 (m, 2H; OeCHHeC, OeCHHeCH),
3.91e3.84 (m, 2H; OeCHHeCH, CH2eCHeCH), 3.69 (s, 1H; OeCH3);
13C NMR (75 MHz, CDCl3): 167.6, 150.3, 143.2 137.6, 131.8, 128.7,
128.5, 127.7, 119.8, 116.2, 74.2, 71.2, 51.5, 46.6; FT-IR (neat): nmax
4.2.7. Compound 3bc. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.51
(d, J¼15.9 Hz, 1H; CeCHeCH), 7.40 (d, J¼7.5 Hz, 2H; AreH), 7.03 (d,
J¼7.5 Hz, 2H; AreH), 5.96e5.85 (m, 1H; CHeCHeCH2), 5.30e5.21
(m, 2H; CHeCH2), 4.82 (d, J¼15.9 Hz, 1H; CHeCHeCN), 4.23 (d,
J¼15.9 Hz, 1H; OeCHHeC), 4.09e4.01 (m, 2H; OeCHHeC,
OeCHHeCH), 3.88e3.85 (m, 1H; OeCHHeCH), 3.74 (m, 1H;
CH2eCHeCH); 13C NMR (75 MHz, CDCl3): 152.1, 148.1, 136.9, 134.4,
134.3, 130.4, 130.1, 129.5, 118.3, 116.9, 98.2, 74.3, 71.4, 46.9; FT-IR
3080, 3028, 1714, 1633, 1288, 1170, 1103, 1064, 736, 704 cmꢁ1
;
HRMS: calcd for C17H19O3 [MþH]þ 271.1329; found 271.1326.
(neat): nmax 3082, 3028, 2216, 1635, 1593, 1105, 1062, 839 cmꢁ1
HRMS: calcd for C16H15ClNO [MþH]þ 272.0837; found 272.0839.
;
4.2.2. Compound 3ab. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.82
(d, J¼15.6 Hz, 1H; CeCHeCH), 7.37e7.31 (m, 3H; AreH), 7.09e7.07
(m, 2H; AreH), 5.97e5.89 (m, 1H; CHeCHeCH2), 5.37 (d, J¼15.6 Hz,
1H; CHeCHeCO), 5.30e5.19 (m, 2H; CHeCH2), 4.25 (d, J¼15.9 Hz,
1H; OeCHHeC), 4.18e4.02 (m, 4H; OeCHHeC, OeCHHeCH,
OeCH2eCH3), 3.89e3.83 (m, 2H; OeCHHeCH, CH2eCHeCH), 1.23
(t, J¼6.6 Hz, 3H; CH2eCH3); 13C NMR (75 MHz, CDCl3): 167.3, 150.2,
143.0, 137.7, 137.6, 131.9, 128.8, 128.6, 127.7, 120.3, 116.3, 74.2, 71.3,
60.3, 14.2; FT-IR (neat): nmax 3080, 3028, 1714, 1633, 1286, 1172,
1101, 1064, 734, 702 cmꢁ1; HRMS: calcd for C18H21O3 [MþH]þ
285.1485; found 285.1479.
4.2.8. Compound 3bd. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.39
(d, J¼7.8 Hz, 2H; AreH), 7.30e7.14 (m, 6H; AreH; CeCHeCH), 7.13
(d, J¼7.5 Hz, 2H; AreH), 6.01e5.96 (m, 2H; CHeCHeCH2, CeCHeC),
5.34e5.21 (m, 2H; CHeCH2), 4.23 (d, J¼15.0 Hz, 1H; OeCHHeC),
4.11e4.03 (m, 2H; OeCHHeC, OeCHHeCH), 3.88e3.81 (m, 2H;
OeCHHeCH, CH2eCHeCH); 13C NMR (75 MHz, CDCl3): 142.2, 138.4,
137.4, 137.3, 133.2, 132.4, 131.1, 130.4, 128.9, 128.6, 127.8, 127.6, 126.4,
115.8, 74.4, 71.2, 46.8; FT-IR (neat): nmax 3078, 3030, 1639, 1593,
1105, 829, 746, 700 cmꢁ1; HRMS: calcd for C21H20ClO [MþH]þ
323.1197; found 323.1181.
4.2.3. Compound 3ac. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.53
(d, J¼15.9 Hz, 1H; CeCHeCH), 7.38 (m, 3H; AreH), 7.08 (m, 2H;
AreH), 5.95e5.87 (m, 1H; CHeCHeCH2), 5.27e5.22 (m, 2H;
CHeCH2), 4.83 (d, J¼15.9 Hz, 1H; CHeCHeCN), 4.24 (d, J¼15.9 Hz,
1H; OeCHHeC), 4.08e4.03 (m, 2H; OeCHHeC, OeCHHeCH),
3.88e3.86 (m, 1H; OeCHHeCH), 3.74 (m, 1H; CH2eCHeCH); 13C
NMR (75 MHz, CDCl3): 151.5, 148.5, 137.2, 135.9, 131.6, 129.1, 128.6,
128.3, 118.6, 116.8, 98.3, 74.4, 71.5, 46.9; FT-IR (neat): nmax 3080,
3028, 2214, 1633, 1593, 1105, 1064, 707 cmꢁ1; HRMS: calcd for
C16H16NO [MþH]þ 238.1226; found 238.1222.
4.2.9. Compound 3ca. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.81
(d, J¼15.6 Hz, 1H; CeCHeCH), 7.01 (d, J¼8.4 Hz, 2H; AreH), 6.90 (d,
J¼8.1 Hz, 2H; AreH), 5.97e5.89 (m, 1H; CHeCHeCH2), 5.43 (d,
J¼15.3 Hz, 1H; CHeCHeCO), 5.29e5.19 (m, 2H; CHeCH2), 4.28 (d,
J¼16.2 Hz, 1H; OeCHHeC), 4.10e4.02 (m, 2H; OeCHHeC,
OeCHHeCH), 3.89e3.83 (m, 5H; OeCHHeCH, CH2eCHeCH,
OeCH3), 3.70 (s, 3H; OeCH3); 13C NMR (75 MHz, CDCl3): 167.7,
158.9, 150.3, 143.6, 137.7, 131.5, 129.8, 119.7, 116.2, 114.1, 74.2, 71.4,
55.3, 51.6, 46.7; FT-IR (neat): nmax 3078, 3034, 1714, 1633, 1288,
1246,1170,1101,1064, 837 cmꢁ1; HRMS: calcd for C18H21O4 [MþH]þ
301.1434; found 301.1426.
4.2.4. Compound 3ad. Yellow oil; 1H NMR (300 MHz, CDCl3):
d
7.46e7.19 (m, 11H; CeCHeCH, AreH), 6.07e5.99 (m, 2H;
CHeCHeCH2, CHeCHeC), 5.37e5.22 (m, 2H; CHeCH2), 4.27 (d,
J¼15.0 Hz, 1H; OeCHHeC), 4.13e4.07 (m, 2H; OeCHHeC,
OeCHHeCH), 3.90e3.84 (m, 2H; OeCHHeCH, CH2eCHeCH); 13C
NMR (75 MHz, CDCl3): 141.7, 139.0, 138.6, 137.5, 133.5, 130.9, 128.9,
128.6, 128.2, 127.5, 127.3, 126.4, 115.7, 74.4, 71.4, 46.7. FT-IR (neat):
4.2.10. Compound 3cb. Yellow oil; 1H NMR (300 MHz, CDCl3):
d
7.82 (d, J¼15.6 Hz, 1H; CCH), 7.01 (d, J¼7.8 Hz, 2H; AreH), 6.90 (d,
J¼8.1 Hz, 2H; AreH), 5.99e5.88 (m, 1H; CHeCHeCH2), 5.42 (d,
J¼15.3 Hz, 1H; CHeCHeCO), 5.30e5.19 (m, 2H; CHeCH2), 4.28 (d,
J¼15.6 Hz, 1H; OeCHHeC), 4.19e4.03 (m, 4H; OeCHHeC,

8714
T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
OeCHHeCH, OeCH2eCH3), 3.89e3.83 (m, 5H; OeCHHeCH,
CH2eCHeCH, OeCH3), 1.25 (t, J¼6.9 Hz, 3H); 13C NMR (75 MHz,
CDCl3): 167.3, 158.9, 150.2, 143.4, 137.7, 131.5, 129.8, 120.2, 116.2,
114.1, 74.2, 71.4, 60.3, 55.2, 46.7, 14.2; FT-IR (neat): nmax 3078, 3034,
1714, 1633, 1286, 1246, 1174, 1101, 1064, 837 cmꢁ1; HRMS: calcd for
C19H23O4 [MþH]þ 315.1591; found 315.1580.
812 cmꢁ1; HRMS: calcd for C23H23N2O2S [MþH]þ 391.1475; found
391.1461.
4.2.16. Compound 3dd. White solid. Mp 135e137 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
7.62 (d, J¼7.5 Hz, 2H; AreH), 7.42e7.06 (m,
13H; AreH, CeCHeCH), 5.97 (d, J¼15.9 Hz, 1H; CHeCHeC),
5.90e5.82 (m, 1H; CHeCHeCH2), 5.27e5.14 (m, 2H; CHeCH2),
3.82e3.77 (m, 2H; CH2eCHeCH, NeCHHeC), 3.50e3.38 (m, 3H;
NeCHHeC, NeCH2eCH), 2.44 (s, 3H; CeCH3); 13C NMR (75 MHz,
CDCl3): 143.7, 138.5, 137.8, 137.2, 136.9, 135.8, 132.2, 131.9, 129.7,
128.8, 128.7, 128.6, 127.9, 127.7, 127.5, 127.1, 126.4, 115.9, 53.9, 51.7,
44.8, 21.6; FT-IR (KBr): nmax 3076, 3027, 1597, 1336, 1153, 817, 750,
700 cmꢁ1; HRMS: calcd for C28H28NO2S [MþH]þ 442.1835; found
442.1792.
4.2.11. Compound 3cc. Yellow oil; 1H NMR (300 MHz, CDCl3):
d 7.52
(d, J¼15.9 Hz, 1H; CeCHeCH), 7.00 (d, J¼8.1 Hz, 2H; AreH), 6.92 (d,
J¼9.0 Hz, 2H; AreH), 5.97e5.86 (m, 1H; CHeCHeCH2), 5.26e5.21
(m, 2H; CHeCH2), 4.87 (d, J¼15.9 Hz, 1H; CHeCHeCN), 4.25 (d,
J¼16.2 Hz, 1H; OeCHHeC), 4.09e4.04 (m, 2H; OeCHHeC,
OeCHHeCH), 3.88e3.83 (m, 4H; OeCHHeCH, OeCH3), 3.78e3.73
(m, 1H; CH2eCHeCH); 13C NMR (75 MHz, CDCl3): 159.3, 151.4,
148.8, 137.3, 131.2, 129.8, 128.1, 118.7, 116.7, 114.4, 97.8, 74.3, 71.5,
55.3, 46.9; FT-IR (neat): nmax 3078, 3034, 2214, 1633, 1593, 1247,
4.2.17. Compound 3ea. White solid. Mp 122e124 ꢀC; 1H NMR
1105, 1064, 839 cmꢁ1
268.1332; found 268.1332.
;
HRMS: calcd for C17H18NO2 [MþH]þ
(300 MHz, CDCl3):
d
7.71 (d, J¼7.5 Hz, 2H; AreH), 7.43 (d, J¼15.9 Hz,
1H; CeCHeCH), 7.34 (d, J¼7.5 Hz, 2H; AreH), 5.83 (d, J¼15.9 Hz,1H;
CHeCHeCO), 5.77e5.69 (m, 1H; CHeCHeCH2), 5.08e5.03 (m, 2H;
CHeCH2), 4.09 (d, J¼15.9 Hz, 1H; NeCHHeC), 3.77e3.66 (m, 5H;
NeCHHeC, CH2eCHeCH, OeCH3), 3.45e3.41 (m, 1H; NeCHHeCH),
3.19e3.14 (m, 1H; NeCHHeCH), 2.44 (s, 3H; CeCH3), 2.08e2.04 (m,
2H; CeCH2eCH2), 1.31e1.30 (m, 4H; CH2eCH2eCH2eCH3), 0.90 (m,
3H; CH2eCH3); 13C NMR (75 MHz, CDCl3): 167.6, 144.1, 143.9, 141.4,
137.2, 132.0, 131.4, 129.7, 127.9, 117.2, 116.1, 53.5, 51.6, 50.8, 44.8,
30.4, 29.5, 22.9, 21.6, 13.9; FT-IR (KBr): nmax 3076, 3026, 1710, 1344,
1286, 1168, 1091, 817 cmꢁ1; HRMS: calcd for C22H30NO4S [MþH]þ
404.1890; found 404.1873.
4.2.12. Compound 3cd. Yellow oil; 1H NMR (300 MHz, CDCl3):
7.31e7.20 (m, 6H; CeCHeCH, AreH), 7.11 (d, J¼7.8 Hz, 2H; AreH),
d
6.95 (d, J¼6.9 Hz, 2H; AreH), 6.09e5.95 (m, 2H; CHeCHeCH2,
CHeCHeC), 5.35e5.21 (m, 2H; CHeCH2), 4.28 (d, J¼15.0 Hz, 1H;
OeCHHeC), 4.13e4.08 (m, 2H; OeCHHeC, OeCHHeCH), 3.86e3.82
(m, 5H; OeCHHeCH, CH2eCHeCH, OeCH3); 13C NMR (75 MHz,
CDCl3): 158.6, 141.8, 138.7, 137.6, 133.1, 131.3, 130.8, 130.1, 128.6,
128.5, 127.4, 126.4, 115.6, 113.9, 74.4, 71.4, 55.2, 46.7; FT-IR (neat):
nmax 3078, 3032,1635,1608,1246,1031,1107, 756, 694 cmꢁ1; HRMS:
calcd for C22H23O2 [MþH]þ 319.1693; found 319.1681.
4.2.18. Compound 3ec. White solid. Mp 105e106 ꢀC; 1H NMR
4.2.13. Compound 3da. White solid. Mp 151e152 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
7.70 (d, J¼6.6 Hz, 2H; AreH), 7.34 (d,
(300 MHz, CDCl3):
d
7.69e7.58 (m, 3H; CeCHeCH, AreH), 7.36e7.26
J¼6.6 Hz, 2H; AreH), 7.11 (d, J¼16.8 Hz, 1H; CeCHeCH),
5.77e5.66 (m, 1H; CHeCHeCH2), 5.27 (d, J¼16.8 Hz, 1H;
CHeCHeCN), 5.09e4.96 (m, 2H; CHeCH2), 4.07 (d, J¼16.8 Hz, 1H;
NeCHHeC), 3.73 (d, J¼16.5 Hz, 1H; NeCHHeC), 3.55 (m, 1H;
CH2eCHeCH), 3.41e3.38 (m, 1H; NeCHHeCH), 3.19e3.14 (m, 1H;
NeCHHeCH), 2.43 (s, 3H; CeCH3), 2.04 (m, 2H; CeCH2eCH2), 1.29
(m, 4H; CH2eCH2eCH2eCH3), 0.90 (m, 3H; CH2eCH3); 13C NMR
(75 MHz, CDCl3): 146.9, 145.4, 144.2, 136.9, 131.8, 131.1, 129.8,
127.9, 118.5, 116.7, 95.7, 53.7, 51.0, 44.9, 30.2, 28.8, 22.9, 21.6, 13.9;
FT-IR (KBr): nmax 3084, 3034, 2210, 1631, 1595, 1346, 1157,
817 cmꢁ1; HRMS: calcd for C21H27N2O2S [MþH]þ 371.1788; found
371.1778.
(m, 5H; AreH), 6.98 (m, 2H; AreH), 5.85e5.79 (m, 1H;
CHeCHeCH2), 5.34 (d, J¼15.0 Hz, 1H; CHeCHeCO), 5.23e5.13 (m,
2H; CHeCH2), 3.85e3.79 (m, 2H; CH2eCHeCH, NeCHHeC), 3.67 (s,
3H; OeCH3), 3.47e3.41 (m, 2H; NeCHHeC, NeCHHeCH),
3.33e3.30 (m, 1H; NeCHHeCH), 2.43 (s, 3H; CeCH3); 13C NMR
(75 MHz, CDCl3): 167.4, 145.4, 143.9, 141.9, 136.9, 134.1, 132.1, 129.7,
128.9, 128.4, 128.0, 127.8, 120.8, 116.5, 53.6, 51.8, 51.6, 44.9, 21.6; FT-
IR (KBr): nmax 3084, 3034, 1712, 1633, 1598, 1344, 1284, 1157, 1089,
816 cmꢁ1; HRMS: calcd for C24H26NO4S [MþH]þ 424.1577; found
424.1574.
4.2.14. Compound 3db. White solid. Mp 134e135 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
7.67 (d, J¼15.6 Hz, 1H; CeCHeCH), 7.60 (d,
4.2.19. Compound 3ed. White solid. Mp 90e91 ꢀC; 1H NMR
J¼7.2 Hz, 2H; AreH), 7.36e7.26 (m, 5H; AreH), 6.98 (d, J¼5.1 Hz,
2H; AreH), 5.85e5.79 (m, 1H; CHeCHeCH2), 5.33 (d, J¼15.6 Hz,1H;
CHeCHeCO), 5.23e5.13 (m, 2H; CHeCH2), 4.12 (d, J¼7.2 Hz, 2H;
OeCH2eCH3), 3.85e3.79 (m, 2H; CH2eCHeCH, NeCHHeC),
3.47e3.40 (m, 2H; NeCHHeC, NeCHHeCH), 3.34e3.29 (m, 1H;
NeCHHeCH), 2.43 (s, 3H; CeCH3), 1.22 (d, J¼6.6 Hz, 3H; CH2eCH3);
13C NMR (75 MHz, CDCl3): 166.9, 145.2, 143.9, 141.8, 137.0, 134.2,
132.1, 129.7, 128.9, 128.5, 127.9, 127.8, 121.3, 116.5, 64.4, 53.6, 51.8,
44.9, 21.6, 14.2; FT-IR (KBr): nmax 3076, 3026, 1712, 1340, 1284, 1176,
1157, 1091, 816, 705 cmꢁ1; HRMS: calcd for C25H28NO4S [MþH]þ
438.1734; found 438.1702.
(300 MHz, CDCl3):
d
7.73 (d, J¼6.6 Hz, 2H; AreH), 7.36e7.17 (m, 7H;
AreH), 6.85 (d, J¼16.2 Hz, 1H; CeCHeCH), 6.49 (d, J¼16.2 Hz, 1H;
CHeCHeC), 5.84e5.72 (m, 1H; CHeCHeCH2), 5.12e5.04 (m, 2H;
CHeCH2), 4.08 (d, J¼15.0 Hz,1H; NeCHHeC), 3.78 (d, J¼15.0 Hz,1H;
NeCHHeC), 3.66e3.61 (m, 1H; CH2eCHeCH), 3.42e3.37 (m, 1H;
NeCHHeCH), 3.23e3.17 (m, 1H; NeCHHeCH), 2.43 (s, 3H;
CeCH3), 2.23e2.15 (m, 2H; CeCH2eCH2), 1.41e1.32 (m, 4H;
CH2eCH2eCH2eCH3), 0.93 (m, 3H; CH2eCH3); 13C NMR (75 MHz,
CDCl3): 143.8, 138.1, 137.6, 135.8, 132.9, 132.3, 129.7, 128.7, 127.9,
127.5, 126.3, 126.1, 115.5, 53.8, 50.8, 44.8, 30.8, 29.6, 23.0, 21.6, 14.0;
FT-IR (KBr): nmax 3084, 3034, 2210, 1631, 1597, 1344, 1157, 707 cmꢁ1
.
HRMS: calcd for C26H32NO2S [MþH]þ 422.2148; found 422.2145.
4.2.15. Compound 3dc. White solid. Mp 150e151 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
7.60 (d, J¼7.5 Hz, 2H; AreH), 7.39e7.26 (m, 6H;
4.2.20. Compound 3fa. Yellow oil; 1H NMR (300 MHz, CDCl3):
AreH, CeCHeCH), 6.97 (d, J¼6.4 Hz, 2H; AreH), 5.84e5.75 (m, 1H;
CHeCHeCH2), 5.20e5.15 (m, 2H; CHeCH2), 4.78 (d, J¼15.9 Hz, 1H;
CHeCHeCN), 3.82e3.69 (m, 2H; CH2eCHeCH, NeCHHeC),
3.47e3.30 (m, 3H; NeCHHeC, NeCH2eCH,), 2.44 (s, 3H; CeCH3);
13C NMR (75 MHz, CDCl3): 147.3, 146.6, 144.1, 136.6, 135.4, 133.8,
131.9, 129.8, 129.3, 128.6, 128.5, 127.9, 118.2, 117.1, 99.1, 53.8, 51.9,
45.1, 21.6; FT-IR (KBr): nmax 3084, 3034, 2214, 1597, 1344, 1157,
d
7.78 (d, J¼15.9 Hz, 1H; CeCHeCH), 7.35e7.27 (m, 3H; AreH), 7.09
(m, 2H; AreH), 5.98e5.87 (m, 1H; CHeCHeCH2), 5.42 (d, J¼15.9 Hz,
1H; CHeCHeCO), 5.24e5.16 (m, 2H; CHeCH2), 4.05e3.92 (m, 2H;
NeCH2eC), 3.70e3.54 (m, 6H; NeCH2eCH, CH2eCHeCH, OeCH3),
1.42 (s, 9H; C(CH3)3); 13C NMR (75 MHz, CDCl3): 167.6, 154.4, 147.1,
142.4, 137.9, 137.3, 133.4, 128.8, 128.7, 127.8, 120.4, 115.5, 79.8, 51.5,
49.9, 44.8, 43.8, 28.4; FT-IR (neat): nmax 3093, 3062, 2978, 1714,

T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
8715
1697, 1400, 1288, 1166, 702 cmꢁ1; HRMS: calcd for C22H28NO4
700 cmꢁ1; HRMS: calcd for C22H23O [MþH]þ 303.1743; found
[MþH]þ 370.1974; found 370.1968.
303.1712.
4.2.21. Compound 3fb. Yellow oil; 1H NMR (300 MHz, CDCl3):
d
7.79
4.2.27. Compound 3hc. Yellow oil; 1H NMR (300 MHz, CDCl3):
(d, J¼15.6 Hz, 1H; CeCHeCH), 7.35e7.27 (m, 3H; AreH), 7.09 (m,
2H; AreH), 5.98e5.87 (m, 1H; CHeCHeCH2), 5.41 (d, J¼15.6 Hz, 1H;
CHeCHeCO), 5.24e5.15 (m, 2H; CHeCH2), 4.15 (q, J¼6.9 Hz, 2H;
OeCH2eCH3), 4.04e3.92 (m, 2H; NeCH2eC), 3.69e3.54 (m, 3H;
NeCH2eCH, CH2eCHeCH), 1.42 (s, 9H; C(CH3)3), 1.24 (t, J¼6.9 Hz,
3H; CH2eCH3); 13C NMR (75 MHz, CDCl3): 167.3, 154.4, 146.9, 142.2,
137.9, 137.4, 133.6, 128.8, 128.6, 127.7, 120.8, 115.4, 79.7, 60.3, 51.5,
49.9, 44.6, 28.4, 14.2; FT-IR (neat): nmax 3093, 3062, 2978, 1712,
1695, 1404, 1288, 1163, 705 cmꢁ1; HRMS: calcd for C23H30NO4
[MþH]þ 384.2130; found 384.2124.
d
7.57 (d, J¼15.9 Hz, 1H; CeCHeCH), 7.39e7.32 (m, 3H; AreH),
7.09e7.07 (m, 2H; AreH), 5.96e5.88 (m, 1H; CHeCHeCH2),
5.29e5.19 (m, 2H; CHeCH2), 4.80 (d, J¼16.2 Hz, 1H; CHeCHeCN),
4.52e4.50 (m, 1H; OeCH(C2H5)eC), 4.09e4.04 (m, 1H;
CH2eCHeCH), 3.78e3.73 (m, 2H; OeCH2eCH), 1.11e1.04 (m, 2H;
CHeCH2eCH3), 0.69e0.65 (m, 3H; CH2eCH3); 13C NMR (75 MHz,
CDCl3): 154.8, 149.7, 138.3, 135.9, 132.0, 129.2, 128.9, 128.2, 118.6,
116.4, 97.9, 82.2, 71.4, 47.8, 24.2, 9.9; FT-IR (neat): nmax 3078, 3030,
2214, 1633, 1591, 1120, 1056, 707 cmꢁ1; HRMS: calcd for C18H20NO
[MþH]þ 266.1539; found 266.1538.
4.2.22. Compound 3fc. Yellow oil; 1H NMR (300 MHz, CDCl3):
d
7.50
4.2.28. Compound 3ic. White solid. Mp 166e167 ꢀC; 1H NMR
(d, J¼16.2 Hz, 1H; CeCHeCH), 7.40e7.38 (m, 3H; AreH), 7.08e7.06
(m, 2H; AreH), 5.97e5.88 (m, 1H; CHeCHeCH2), 5.22e5.17 (m, 2H;
CHeCH2), 4.86 (d, J¼16.2 Hz, 1H; CHeCHeCN), 4.03e3.97 (m, 1H;
NeCHHeC), 3.81 (m, 1H; CH2eCHeCH), 3.69e3.61 (m, 3H;
NeCHHeC;; NeCH2eCH), 1.42 (s, 9H; C(CH3)3); 13C NMR (75 MHz,
CDCl3): 154.3, 147.8, 137.5, 135.8, 133.2, 129.2, 128.7, 128.3, 118.5,
115.9, 98.6, 79.9, 51.6, 50.0, 44.9, 28.4; FT-IR (neat): nmax 3084, 3057,
(300 MHz, CDCl3):
d
7.64 (d, J¼7.5 Hz, 2H; AreH), 7.40e7.28 (m, 6H;
AreH, CeCHeCH), 6.86 (d, J¼4.5 Hz, 2H; AreH), 5.93e5.85 (m, 1H;
CHeCHeCH2), 5.24e5.18 (m, 2H; CHeCH2), 4.70 (d, J¼16.2 Hz, 1H;
CHeCHeCN), 4.13 (d, J¼6.0 Hz, 1H; NeCH(CH3)eC), 3.55 (m, 3H;
NeCH2eCH, CH2eCHeCH), 2.47 (s, 3H; CeCH3), 1.13 (d, J¼6.3 Hz,
3H; CHeCH3); 13C NMR (75 MHz, CDCl3): 151.5, 147.9, 143.9, 137.3,
134.9, 133.8, 133.2, 129.7, 129.2, 129.0, 128.5, 127.7, 118.2, 117.3, 99.4,
59.1, 52.6, 44.5, 21.6, 21.5; FT-IR (KBr): nmax 3084, 3034, 2220, 1635,
1591, 1344, 1159, 813 cmꢁ1; HRMS: calcd for C24H25N2O2S [MþH]þ
405.1631; found 405.1627.
2989, 2214, 1697, 1392, 1163, 707 cmꢁ1
; HRMS: calcd for
C21H25N2O2 [MþH]þ 337.1871; found 337.1867.
4.2.23. Compound 3fd. Yellow oil; 1H NMR (300 MHz, CDCl3):
7.40e7.19 (m, 11H; AreH, CeCHeCH), 6.08e5.98 (m, 2H;
d
Acknowledgements
CHeCHeC, CHeCHeCH2), 5.29e5.16 (m, 2H; CHeCH2), 4.03e3.91
(m, 2H; NeCH2eC), 3.70e3.62 (m, 3H; NeCH2eCH, CH2eCHeCH),
1.44 (s, 9H; C(CH3)3); 13C NMR (75 MHz, CDCl3): 154.5, 138.8, 138.6,
137.5, 135.1, 131.5, 129.0, 128.6, 128.3, 127.5, 127.3, 126.4, 114.9, 79.5,
51.7, 49.7, 44.7, 28.5; FT-IR (neat): nmax 3080, 3039, 2974,1689,1400,
1163, 696 cmꢁ1; HRMS: calcd for C26H30NO2 [MþH]þ 388.2232;
found 388.2225.
This research was supported by the National Natural Science
Foundation of China (21072003, 20872002, 21072004, 20832001),
the National Basic Research Program of China (2012CB821604), and
Ministry of Education (20103424110001).
Supplementary data
4.2.24. Compound 3ga. Yellow oil; 1H NMR (300 MHz, CDCl3):
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tet.2011.09.026. These data
include MOL files and InChIKeys of the most important compounds
described in this article.
d
7.83 (d, J¼15.3 Hz, 1H; CeCHeCH), 7.37e7.32 (m, 3H; AreH),
7.10e7.08 (m, 2H; AreH), 6.02e5.90 (m, 1H; CHeCHeCH2), 5.35 (d,
J¼15.6 Hz, 1H; CHeCHeCO), 5.28e5.17 (m, 2H; CHeCH2), 4.72 (m,
1H; OeCH(CH3)eC), 4.13e4.09 (m, 1H; CH2eCHeCH), 3.85e3.79
(m, 2H; OeCH2eCH), 3.69 (s, 3H; OeCH3), 0.80 (d, J¼6.3 Hz, 3H;
CHeCH3); 13C NMR (75 MHz, CDCl3): 167.7,154.8,144.5,138.5,137.4,
132.3, 129.3, 128.7, 127.7, 119.9, 115.8, 76.9, 71.1, 51.5, 47.5, 18.0; FT-IR
(neat): nmax 3080, 3028, 1714, 1278, 1114, 1068, 704 cmꢁ1; HRMS:
calcd for C18H21O3 [MþH]þ 285.1485; found 285.1476.
References and notes
1. (a) Tietze, L. F.; Brasche, G.; Gericke, K. Domino Reactions in Organic Synthesis;
Wiley-VCH: Weinheim, 2006; (b) Tietze, L. F.; Kinzel, T.; Brazel, C. Acc. Chem.
€
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7.54 (d, J¼16.2 Hz, 1H; CeCHeCH), 7.39e7.36 (m, 3H; AreH),
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5.29e5.19 (m, 2H; CHeCH2), 4.85 (d, J¼15.9 Hz, 1H; CHeCHeCN),
4.68 (d, J¼6.3 Hz, 1H; OeCH(CH3)eC), 4.13e4.08 (m, 1H;
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CHeCHeCH2, CHeCHeC), 5.33e5.18 (m, 2H; CHeCH2), 4.73 (d,
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3.85e3.79 (m, 2H; OeCH2eCH), 0.81 (d, J¼6.3 Hz, 3H; CHeCH3);
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129.7, 129.4, 128.6, 128.4, 127.4, 127.2, 126.3, 115.2, 77.0, 71.3, 47.5,
18.6; FT-IR (neat): nmax 3078, 3026, 1635, 1597, 1112, 1070, 754,

8716
T.-jie Meng et al. / Tetrahedron 67 (2011) 8710e8716
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