Tris(4-methoxylphenyl)phosphine-catalyzed C-C bond formation reaction: Mutual addition of aromatic aldehydes and ethyl acrylate

Article abstract of DOI:10.1080/00397911.2011.610551

A highly efficient intermolecular mutual addition of aromatic aldehydes with ethyl acrylate was developed by using tris(4-methoxylphenyl)phosphine as the catalyst. The reaction corresponds to the construction of 1,4-dicarbonyl compound and allylic alcohol

Full text of DOI:10.1080/00397911.2011.610551

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Tris(4-methoxylphenyl)phosphine-
Catalyzed C-C Bond Formation Reaction:
Mutual Addition of Aromatic Aldehydes
and Ethyl Acrylate
Jun-Jiang Teng a , Yan-Hui Qiao a , Qing Zhang a , Chun-Hai Li a & Min
Huang a
a School of Chemistry and Life Science, Guangdong University of
Petrochemical Technology, Maoming, China
Accepted author version posted online: 21 Feb 2012.Version of
record first published: 21 Dec 2012.
To cite this article: Jun-Jiang Teng , Yan-Hui Qiao , Qing Zhang , Chun-Hai Li & Min Huang (2013):
Tris(4-methoxylphenyl)phosphine-Catalyzed C-C Bond Formation Reaction: Mutual Addition of
Aromatic Aldehydes and Ethyl Acrylate, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 43:6, 848-858
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Synthetic Communications1, 43: 848–858, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2011.610551
TRIS(4-METHOXYLPHENYL)PHOSPHINE-CATALYZED
C-C BOND FORMATION REACTION: MUTUAL
ADDITION OF AROMATIC ALDEHYDES AND ETHYL
ACRYLATE
Jun-Jiang Teng, Yan-Hui Qiao, Qing Zhang, Chun-Hai Li,
and Min Huang
School of Chemistry and Life Science, Guangdong University of
Petrochemical Technology, Maoming, China
GRAPHICAL ABSTRACT
Abstract A highly efficient intermolecular mutual addition of aromatic aldehydes with ethyl
acrylate was developed by using tris(4-methoxylphenyl)phosphine as the catalyst. The
reaction corresponds to the construction of 1,4-dicarbonyl compound and allylic alcohol
fragments, which also provides a new way to form C-C bond.
Keywords C-C bond formation; mutual addition; tris(4-methoxylphenyl)phosphine
Received June 14, 2011.
Address correspondence to Jun-Jiang Teng, School of Chemistry and Life Science, Guangdong
University of Petrochemical Technology,
tengjunjiang@yahoo.com.cn
2
Guangdu Road, Maoming 525000, China. E-mail:
848

MUTUAL ADDITION OF AROMATIC ALDEHYDES
849
INTRODUCTION
Carbon–carbon bond formation and the chemical transformations of func-
tional groups along with atom-economical processes have become essential compo-
nents in modern synthetic chemistry.[1–7] A large number of examples have emerged
in the past few decades such as Baylis–Hillman reaction,[8] Stetter reaction,[9] and
benzoin condensation.[10] However, the search for practical organocatalysts without
expensive transition-metal catalytic processes remains of great significance. As we all
known, organophosphorus compounds used as the catalysts have been employed to
construct C-C bonds and functional group transformations.[11] The phenomenal
success of trialkyl=triaryl phosphines in organocatalysis can be attributed primarily
to their pronounced nucleophilicity and the exceptional stability that a phosphonium
ion lends to a neighboring anionic center, leading to Baylis-Hillman-type products
(Scheme 1, I), Stetter-type products (Scheme 1, II), and benzoin condensation
(Scheme 1, III) adducts.[12] Zwitterionic species and phosphonium ylides are
common intermediates in reactions mediated by phosphines.[13] Herein, we report
a novel mutual addition reaction of aromatic aldehydes and ethyl acrylate in the
presence of a catalytic amount of tris(4-methoxylphenyl)phosphine [P(p-PhOCH3)3]
to produce 1,4-dicarbonyl compounds and allylic alcohol derivatives.[14]
RESULTS AND DISCUSSION
We initiated the reaction of ethyl acrylate and 4-nitrobenzaldehyde (1a) in the
presence of triphenylphosphine (PPh3) in dioxane at 60 ꢀC for 24 h, giving ethyl
4-(4-nitrophenyl)-4-oxobutanoate (2a) and (E)-ethyl 4-hydroxy-4-(4-nitrophenyl)-
but-2-enoate (3a) as the major products in 50% total yield (Table 1, entry 1).
Scheme 1. Possible reaction pathways for the reaction of ethyl acrylate with aldehydes.

850
J.-J. TENG ET AL.
Table 1. Condition optimization for the reaction of ethyl acrylate with 4-nitrobenzaldehyde 1aa
Entry
Additive (0.2 equiv.)
Solvent
T (ꢀC)
t (h)
Yield (%)b (2 þ 3)
1
2
PPh3
PPh3
Dioxane
THF
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
70
40
r.t
60
60
60
60
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
15
36
24
24
50
62
3
PPh3
PPh3
Toluene
CH3OH
CH3CN
DMSO
DMF
20
45
4
5
PPh3
PPh3
50
34
6
7
PPh3
PPh3
40
60
8
CHCl3
Cyclohexane
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
9
PPh3
10
10
11
12
13
14
15
16
17
18
19
20
21
22
DABCO
Py
PBu3
None
Trace
70
Et3N
DBU
None
Trace
84
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
P(p-PhOCH3)3
84
39
10
50
84
84
30
aThe reaction was carried out using 0.5 mmol of ethyl acrylate and 0.5 mmol of 1a in solvent (3.0 mL) for
the desired reaction time.
bGC-MS yield.
Encouraged by this result, we next sought to improve upon the efficiency of the reac-
tion in terms of total yields of 2a and 3a. More details of the reaction were investigated
under a variety of reaction conditions. The representative results are summarized in
Table 1. The results indicated that this mutual additional reaction was not sensitive
to the solvent medium (Table 1, entries 1–9), and a relatively greater yield was obtained
in chloroform (CHCl3) (Table 1, entry 8). Among the catalysts examined in CHCl3
(Table 1, entries 10–15), P(p-PhOCH3)3 showed the best result for this transformation
(Table 1, entry 15). The reaction temperature and time had an obvious effect on this
reaction (Table 1, entries 16–20), and the suitable temperature and time were 60ꢀC
and 24h, respectively. Addition of P(p-PhOCH3)3 to the reaction mixture could raise
the yield, and the best result was obtained when the amount of P(p-PhOCH3)3 was 0.2
equiv (Table 1, entries 15, 21, and 22). Thus, the optimized reaction conditions were
established as follows: 0.2 equivalent of P(p-PhOCH3)3, 3 mL CHCl3, 60ꢀC, and 24h.
Experiments that study the scope of this mutual additional reaction were out-
lined in Table 2. Under optimized conditions, a wide range of aromatic aldehydes

MUTUAL ADDITION OF AROMATIC ALDEHYDES
851
Table 2. Scope of the mutual additional reaction of ethyl acrylate with aromatic aldehydes 1a
Entry
1
Yield (%)b (2:3)
80 (36:44)
2
3
70 (32:38)
75 (37:38)
4
5
6
7
8
63 (35:28)
65 (35:30)
62 (40:22)
60 (32:28)
40 (28:12)
9
56 (42:14)
aAll the reactions were carried out using 0.5 mmol of ethyl acrylate, 0.5 mmol of 1, and 0.2 equiv. of P(p-
PhOCH3)3 in dioxane (6.0 mL) at 60 ꢀC for the desired reaction time.
bIsolated yield.
1a–i underwent reactions with ethyl acrylate, affording the corresponding mutual
additional products 2a–i and 3a–i in reasonable yields (Table 2, entries 1–9). The
electronic contribution of the substituents on the aromatic aldehydes (Table 2,
entries 1–9) has significant effect on the reaction. As shown in Table 2, aromatic
aldehydes bearing the meta- and para-electron-withdrawing groups proceed
smoothly and afforded the desired products in good yields (Table 2, entries 1–3),
while para-halogens or meta- and para-electron-donating substituted aromatic
aldehydes gave modetate yields (Table 2, entries 4–9). To our surprise, but-3-en-2-
one as a partner of ethyl acrylate with 4-bromobenzaldehyde under the optimized
reaction conditions gave only traces of 1-(4-bromophenyl)pentane-1,4-dione 4 and

852
J.-J. TENG ET AL.
Scheme 2. A special case for the mutual addition reaction.
(E)-5-(4-bromophenyl)-5-hydroxypent-3-en-2-one 5 in 65% gas chromatography
(GC) yield (Scheme 2).
The rational reaction pathways and mechanisms of ethyl acrylate with
aldehydes in the reaction conditions are depicted in Scheme 1.[15] Although there are
many reports for the application of organophosphorus catalyst in the Baylis–Hillman
reaction, Stetter reaction, and benzoin condensation reaction,[16] it is interesting to
note that, in our reaction conditions, the reaction afforded neither Baylis–Hillman-
type products I nor benzoin condensation adducts III, but only the Stetter-type pro-
ducts II and the allylic alcohol derivatives IV. It is the first time that the Stetter-type
product (Scheme 1, II) and allylic alcohol derivatives (Scheme 1, IV) were the main
products in the same reaction. Moreover, tris(4-methoxylphenyl)phosphine-catalyzed
Baylis–Hillman reaction, Stetter reaction, and benzoin condensation reaction have not
been reported in the literature.
As shown in Scheme 1, the reversible addition reactions of tris(4-methoxylphe-
nyl)phosphine either to aldehyde (1, 2-addition, part 2 and part 3 in Scheme 1) or
ethyl acrylate (1,4-addition, part 1 and part 4 in Scheme 1) might be a competitive
process. The nucleophilic P(p-PhOCH3)3 attacked the carbonyl group to generate
the tautomeric betaine(A)-a-oxo-ylide(B) species, and a-oxo-ylide(B) was added to
ethyl acrylate and gave the Stetter-type products II after regenerating P(p-PhOCH3)3
(part 2 in Scheme 2). Besides, accompanying 1,4-addition of P(p-PhOCH3)3 toward
ethyl acrylate under the employed reaction conditions to form tautomers C–F,
tautomer F attacked the aldehyde, followed by the elimination of P(p-PhOCH3)3 to
afford the allylic alcohol derivatives.
CONCLUSION
In summary, we have disclosed a novel tris(4-methoxylphenyl)phosphine-
catalyzed atom-economical reaction that allows efficient and rapid access to diverse
1,4-dicarbonyl compounds and allylic alcohol derivatives from simple and readily avail-
able starting materials under mild conditions. Further studies on the general application
of various unsaturated acryl compounds and intramolecular coupling are ongoing.
EXPERIMENTAL
Typical Reaction
A round-bottomed flask was charged with ethyl acrylate (50 mg, 0.5 mmol),
4-nitrobenzaldehyde (1a, 76 mg, 0.5 mmol), 3 mL chloroform (CHCl3), and tris(4-
methoxylphenyl)phosphine [P(p-PhOCH3)3] (35.2 mg, 0.1 mmol). The mixture was
stirred at 60 ꢀC for 24 h. After cooling, the resulting mixture was then detected by

MUTUAL ADDITION OF AROMATIC ALDEHYDES
853
gas chromatography (GC) and GC-MS. The solvent was removed under reduced
pressure and the crude product was subjected to isolation by preparative thin layer
chromatography (PTLC) (GF254) and eluted with a 10:1 petroleum ether–diethyl
ether mixture to afford the desired products ethyl 4-(4-nitrophenyl)-4-oxobutanoate
(2a) and (E)-ethyl 4-hydroxy-4-(4-nitrophenyl)but-2-enoate (3a).
Ethyl 4-(4-Nitrophenyl)-4-oxobutanoate (Table 2, Entry 1, 2a)
Pale yellow viscous oil; IR vmax (KBr): 1733, 1695, 1615, 1525, 1370, 1210,
1
1096, 853, 744 cmꢁ1; H NMR (400 MHz, CDCl3): d 8.31 (d, 2H), 8.13 (d, 2H),
4.13 (q, 2H), 3.31 (t, 2H), 2.78 (t, 2H), 1.25 (t, 3H); 13C NMR (100 MHz, CDCl3):
d 196.8, 172.5, 150.4, 141.0, 129.1, 123.9, 60.9, 33.9, 28.1, 14.2; GC-MS m=z (%
rel. inten.): 251.03 (Mþ, 14.17), 149.89 (100). Anal. calcd. for C12H13NO5: C,
57.83; H, 4.45; Found: C, 57.42; H, 5.50.
(E)-Ethyl 4-Hydroxy-4-(4-nitrophenyl)but-2-enoate (Table 2,
Entry 1, 3a)
Pale yellow viscous oil; IR vmax (KBr): 3500, 1712, 1635, 1538, 1470, 1434,
1
1350, 1224, 1157, 1050, 970, 886, 695 cmꢁ1; H NMR (400 MHz, CDCl3): d 8.19
(d, 2H), 7.54 (d, 2H), 6.37 (s, 1H), 5.82 (s, 1H), 5.60 (d, 2H), 4.17 (q, 2H), 3.38 (s,
1H), 1.25 (t, 3H); 13C NMR (100 MHz, CDCl3): d 166.0, 148.6, 147.4, 141.1,
127.3, 127.1, 123.6, 72.9, 61.3, 14.0; GC-MS m=z (% rel. inten.): 251.02 (Mþ,
4.09), 149.84 (100). Anal. calcd. for C12H13NO5: C, 57.83; H, 4.45. Found: C,
57.60; H, 4.35.
Ethyl 4-(3-Nitrophenyl)-4-oxobutanoate (Table 2, Entry 2, 2b)
Pale yellow viscous oil; IR vmax (KBr): 1720, 1685, 1602, 1521, 1378, 1211,
1
1091,948, 882, 735, 672 cmꢁ1; H NMR (400 MHz, CDCl3): d 8.79 (s, 1H), 8.42
(d, 1H), 8.30 (d, 1H), 7.65 (t, 1H), 4.15 (q, 2H), 3.33 (t, 2H), 2.79 (t, 2H), 1.25 (t,
3H); 13C NMR (100 MHz, CDCl3): d 196.1, 172.5, 148.4, 137.8, 133.6, 129.9,
127.5, 123.0, 60.9, 33.5, 28.1, 14.2; GC-MS m=z (% rel. inten.): 251.01 (Mþ,
10.27), 149.82 (100). Anal. calcd. for C12H13NO5: C, 57.83; H, 4.45. Found: C,
57.88; H, 4.70.
(E)-Ethyl 4-Hydroxy-4-(3-nitrophenyl)but-2-enoate (Table 2,
Entry 2, 3b)
Orange viscous oil; IR vmax (KBr): 3453, 1715, 1630, 1542, 1380, 1358, 1212,
1065, 970, 740 cmꢁ1; 1H NMR (400 MHz, CDCl3): d 8.23 (s, 1H), 8.13 (d, 1H), 7.73
(d, 1H), 7.52 (t, 1H), 6.39 (s, 1H), 5.86 (s, 1H), 5.59 (d, 1H), 4.17 (q, 2H), 3.34 (d,
1H), 1.25 (t, 3H); 13C NMR (100 MHz, CDCl3): d 165.9, 148.3, 143.7, 141.1,
132.6, 129.3, 127.0, 122.7, 121.5, 72.7, 61.3, 14.0; GC-MS m=z (% rel. inten.):
251.02 (Mþ, 4.01), 149.63 (100). Anal. calcd. for C12H13NO5: C, 57.83; H, 4.45.
Found: C, 57.82; H, 4.68.

854
J.-J. TENG ET AL.
Ethyl 4-Oxo-4-(3-(trifluoromethyl)phenyl)butanoate (Table 2,
Entry 3, 2c)
Pale yellow viscous oil; IR vmax (KBr): 1734, 1696, 1615, 1373, 1330, 1127,
1
1072, 942, 806, 695 cmꢁ1; H NMR (400 MHz, CDCl3): d 8.21 (s, 1H), 8.15 (d,
1H), 7.81 (d, 1H), 7.58 (t, 1H), 4.15 (q, 2H), 3.30 (t, 2H), 2.76 (t, 2H), 1.25 (t, 3H);
13C NMR (100 MHz, CDCl3): d 196.9, 172.7, 137.1, 131.2, 129.6, 129.3, 124.9,
124.9, 60.8, 33.5, 28.1, 14.2; GC-MS m=z (% rel. inten.): 273.97 (Mþ, 19.37),
172.75 (100). Anal. calcd. for C13H11F3O3: C, 57.36; H, 4.07. Found: C, 57.40; H,
4.27.
(E)-Ethyl 4-Hydroxy-4-(3-(trifluoromethyl)phenyl)but-2-enoate
(Table 2, Entry 3, 3c)
Orange viscous oil; IR vmax (KBr): 3425, 1713, 1632, 1449, 1372, 1163, 1073,
1
960, 806, 703 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.63 (s, 1H), 7.54–7.42 (m, 3H),
6.36 (s, 1H), 5.80 (s, 1H), 5.57 (s, 1H), 4.17 (q, 2H), 3.27 (b, 1H), 1.25 (t, 3H); 13C
NMR (100 MHz, CDCl3): d 166.1, 142.4, 141.5, 129.9, 128.8, 126.7, 124.6, 124.6,
123.4, 123.4, 73.0, 61.2, 14.0; GC-MS m=z (% rel. inten.): 273.91 (Mþ, 6.96), 172.69
(100). Anal. calcd. for C13H11F3O3: C, 57.36; H, 4.07. Found: C, 57.41; H, 4.00.
Ethyl 4-(4-Fluorophenyl)-4-oxobutanoate (Table 2, Entry 4, 2d)
Colorless solid, mp: 56–57 ꢀC; IR vmax (KBr): 1735, 1685, 1598, 1509, 1476,
1
1226, 1029, 989, 838, 745 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.98 (d, 2H), 7.11
(d, 2H), 4.12 (q, 2H), 3.24 (t, 2H), 2.71 (t, 2H), 1.22 (t, 3H); 13C NMR (100 MHz,
CDCl3): d 196.5, 172.8, 132.9, 130.9, 115.5, 114.5, 60.6, 33.2, 28.1, 14.1; GC-MS
m=z (% rel. inten.): 222.23 (Mþ, 50.02), 120.83 (100). Anal. calcd. for C12H11FO3:
C, 64.86; H, 4.99. Found: C, 64.59; H, 4.92.
(E)-Ethyl 4-(4-Fluorophenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 4, 3d)
Colorless viscous oil; IR vmax (KBr): 3428, 1713, 1631, 1605, 1509, 1371, 1223,
1151, 1044, 958, 836, 707 cmꢁ1; 1H NMR (400 MHz, CDCl3): d 7.31 (d, 2H), 7.69 (d,
2H), 6.30 (s, 1H), 5.78 (s, 1H), 5.50 (s, 1H), 4.17 (q, 2H), 2.98 (b, 1H), 1.25 (t, 3H);
13C NMR (100 MHz, CDCl3): d 166.2, 142.1, 137.5, 128.3, 125.8, 115.3, 115.1, 72.5,
61.0, 14.0; GC-MS m=z (% rel. inten.): 224.23 (Mþ, 18.88), 122.79 (100). Anal. calcd.
for C12H11FO3: C, 64.86; H, 4.99. Found: C, 64.88; H, 4.96.
Ethyl 4-(4-Chlorophenyl)-4-oxobutanoate (Table 2, Entry 5, 2e)
Pale yellow solid, mp: 57–59 ꢀC; IR vmax (KBr): 1731, 1671, 1588, 1484, 1400,
1
1319, 1172, 1067, 967, 846, 788 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.90 (d, 2H),
7.39 (d, 2H), 4.11 (q, 2H), 3.24 (t, 2H), 2.72 (t, 2H), 1.23 (t, 3H); 13C NMR
(100 MHz, CDCl3): d 196.9, 172.7, 134.8, 129.4, 128.8, 127.9, 60.7, 33.3, 28.1,

MUTUAL ADDITION OF AROMATIC ALDEHYDES
855
14.1; GC-MS m=z (% rel. inten.): 240.78 (Mþ, 39.66), 139.36 (100). Anal. calcd. for
C12H11ClO3: C, 60.39; H, 4.65. Found: C, 60.44; H, 4.81.
(E)-Ethyl 4-(4-Chlorophenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 5, 3e)
Pale yellow viscous oil; IR vmax (KBr): 3428, 1712, 1633, 1489, 1406, 1371,
1
1150, 1090, 957, 848, 738, 691 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.24 (s, 4H),
6.31 (s, 1H), 5.78 (s, 1H), 5.49 (s, 1H), 4.15 (q, 2H), 2.84 (b, 1H), 1.25 (t, 3H);
13C NMR (100 MHz, CDCl3): d 166.2, 141.8, 139.8, 133.5, 128.5, 127.9, 126.1,
72.7, 61.0, 14.0; GC-MS m=z (% rel. inten.): 240.78 (Mþ, 17.23), 139.31 (100). Anal.
calcd. for C12H11ClO3: C, 60.39; H, 4.65. Found: C, 60.55; H, 4.82.
Ethyl 4-(4-Bromophenyl)-4-oxobutanoate (Table 2, Entry 6, 2f)
Pale yellow solid, mp 61–63 ꢀC; IR vmax (KBr): 1730, 1670, 1582, 1479, 1396,
1320, 1219, 1175, 1068, 968, 949, 844, 767 cmꢁ1; 1H NMR (400 MHz, CDCl3): d 7.83
(d, 2H), 7.59 (d, 2H), 4.12 (q, 2H), 3.24 (t, 2H), 2.73 (t, 2H), 1.24 (t, 3H); 13C NMR
(100 MHz, CDCl3): d 197.1, 172.8, 135.3, 131.9, 129.5, 128.4, 60.7, 33.3, 28.2, 14.2;
GC-MS m=z (% rel. inten.): 283.94 (Mþ, 35.93), 182.78 (100); Anal. calcd. for
C12H11BrO3: C, 50.91; H, 3.92. Found: C, 50.78; H, 3.82.
(E)-Ethyl 4-(4-Bromophenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 6, 3f)
Pale yellow viscous oil; IR vmax (KBr): 3449, 1712, 1632, 1465, 1402, 1371,
1
1269, 1150, 1070, 959, 846, 731, 684 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.44 (d,
2H), 7.24 (d, 2H), 6.31 (s, 1H), 5.78 (s, 1H), 5.48 (s, 1H), 4.15 (q, 2H), 2.70 (b, 1H),
1.25 (t, 3H); 13C NMR (100 MHz, CDCl3): d 166.2, 141.7, 140.4, 131.5, 128.3,
126.2, 121.7, 72.8, 61.1, 14.0; GC-MS m=z (% rel. inten.): 283.86 (Mþ, 8.66), 182.74
(100). Anal. calcd. for C12H11BrO3: C, 50.91; H, 3.92. Found: C, 50.82; H, 3.84.
Ethyl 4-(4-Iodophenyl)-4-oxobutanoate (Table 2, Entry 7, 2g)
Colorless solid; mp 64–66 ꢀC; IR vmax (KBr): 1734, 1688, 1579, 1396, 1372,
1161, 1081, 992, 944, 891, 756, 710, 681 cmꢁ1 1H NMR (400 MHz, CDCl3): d
;
7.81 (d, 2H), 7.65 (d, 2H), 4.11 (q, 2H), 3.23 (t, 2H), 2.72 (t, 2H), 1.25 (t, 3H); 13C
NMR (100 MHz, CDCl3): d 197.3, 172.6, 137.8, 135.7, 129.3, 101.1, 60.5, 33.2,
28.1, 14.1; GC-MS m=z (% rel. inten.): 331.93 (Mþ, 48.98), 230.73 (100). Anal. calcd.
for C12H11IO3: C, 43.66; H, 3.36. Found: C, 43.42; H, 3.32.
(E)-Ethyl 4-(4-Iodophenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 7, 3g)
Colorless viscous oil; IR vmax (KBr): 3442, 1700, 1631, 1481, 1398, 1268, 1149,
1058, 958, 844 cmꢁ1; 1H NMR (400 MHz, CDCl3): d 7.65 (d, 2H), 7.10 (d, 2H), 6.31
(s, 1H), 5.78 (s, 1H), 5.47 (s, 1H), 4.16 (q, 2H), 2.52 (b, 1H), 1.25 (t, 3H); 13C NMR

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J.-J. TENG ET AL.
(100 MHz, CDCl3): d 166.2, 141.7, 141.1, 137.5, 128.5, 126.3, 93.4, 73.0, 61.1, 14.0;
GC-MS m=z (% rel. inten.): 331.78 (Mþ, 16.73), 230.69 (100). Anal. calcd. for
C12H11IO3: C, 43.66; H, 3.36. Found: C, 43.60; H, 3.43.
Ethyl 4-(4-Methoxyphenyl)-4-oxobutanoate (Table 2, Entry 8, 2h)
Pale yellow viscous oil; IR vmax (KBr): 1732, 1678, 1602, 1461, 1364, 1259, 1112,
1032, 986, 800 cmꢁ1; 1H NMR (400 MHz, CDCl3): d 7.96 (d, 2H), 6.90 (d, 2H), 4.14
(q, 2H), 3.85 (s, 3H), 3.24 (t, 2H), 2.72 (t, 2H), 1.24 (t, 3H); 13C NMR (100 MHz,
CDCl3): d 196.7, 173.1, 163.6, 130.3, 129.7, 60.5, 55.5, 33.0, 28.4, 14.2; GC-MS m=z
(% rel. inten.): 235.96 (Mþ, 17.72), 134.79 (100). Anal. calcd. for C13H14O4: C,
66.66; H, 6.02. Found: C, 66.78; H, 6.12.
(E)-Ethyl 4-(4-Methoxyphenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 8, 3h)
Pale yellow viscous oil; IR vmax (KBr): 3425, 1701, 1650, 1511, 1250, 1147,
1
1109, 951, 830 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.28 (d, 2H), 6.84 (d, 2H),
6.30 (s, 1H), 5.80 (s, 1H), 5.50 (s, 1H), 4.14 (q, 2H), 3.78 (s, 1H), 1.25 (t, 3H); 13C
NMR (100 MHz, CDCl3): d 166.4, 159.2, 142.4, 133.5, 127.9, 125.5, 113.8, 72.9,
60.9, 55.3, 14.1; GC-MS m=z (% rel. inten.): 235.89 (Mþ, 5.83), 134.72 (100). Anal.
calcd. for C13H14O4: C, 66.66; H, 6.02. Found: C, 66.80; H, 6.00.
Ethyl 4-(3-Methylphenyl)-4-oxobutanoate (Table 2, Entry 9, 2i)
Pale yellow viscous oil; IR vmax (KBr): 1732, 1679, 1602, 1511, 1461, 1364,
1218, 1112, 1032, 986, 834 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.75 (d, 2H),
;
7.34 (m, 2H), 4.14 (q, 2H), 3.28 (t, 2H), 2.73 (t, 2H), 1.25 (t, 3H); 13C NMR
(100 MHz, CDCl3): d 198.4, 173.0, 138.4, 136.6, 133.9, 128.6, 128.5, 125.2, 60.6,
33.4, 28.3, 21.3, 14.2; GC-MS m=z (% rel. inten.): 220.01 (Mþ, 20.40), 118.81
(100). Anal. calcd. for C13H14O3: C, 71.54; H, 6.47; Found: C, 71.76; H, 6.32.
(E)-Ethyl 4-(3-Methylphenyl)-4-hydroxybut-2-enoate (Table 2,
Entry 9, 3I)
Pale yellow viscous oil; IR vmax (KBr): 3425, 1701, 1650, 1511, 1480, 1250,
1
1147, 951, 830 cmꢁ1; H NMR (400 MHz, CDCl3): d 7.24–7.06 (m, 4H), 6.31 (s,
1H), 5.80 (s, 1H), 5.50 (s, 1H), 4.14 (q, 2H), 2.41 (b, 1H), 2.32 (s, 3H), 1.25 (t, 3H);
13C NMR (100 MHz, CDCl3): d 166.4, 142.1, 141.2, 138.0, 128.5, 128.3, 127.2,
125.8, 123.6, 73.4, 60.9, 21.4, 14.0; GC-MS m=z (% rel. inten.): 219.93 (Mþ, 5.13),
118.85 (100). Anal. calcd. for C13H14O3: C, 71.54; H, 6.47. Found: C, 71.80; H, 6.49.
(E)-5-Hydroxy-5-(4-bromophenyl)pent-3-en-2-one (Scheme 1, 5)
Colorless viscous oil; IR vmax (KBr): 3425, 1670, 1487, 1367, 1073, 954 cmꢁ1
;
1H NMR (400 MHz, CDCl3): d 7.45 (d, 2H), 7.20 (d, 2H), 6.18 (s, 1H), 5.95 (s, 1H),
5.54 (s, 1H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3): d 200.3, 149.5, 140.5, 131.5,

MUTUAL ADDITION OF AROMATIC ALDEHYDES
857
128.2, 127.0, 121.6, 72.3, 18.0; GC-MS m=z (% rel inten.): 253.90 (Mþ, 8.66), 152.52
(100). Anal. calcd. for C11H11BrO2: C, 51.79; H, 4.35. Found: C, 51.60; H, 4.60.
ACKNOWLEDGMENT
The authors thank Guangdong Science and Technology Project (No.
2009B020312016) for the financial support of this work.
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