Study of the reaction of 1,1-bis(trimethylsilyl)-2-phenylethylene with some acyl chlorides in the presence of AlCl3

Article abstract of DOI:10.1016/j.jorganchem.2008.02.032

1,1-Bis(trimethylsilyl)-2-phenylethylene (1), which has been synthesized from the Peterson reaction between (Me₃Si)₃CLi and benzaldehyde, reacts with various acyl chlorides (RCOCl, R = Me, Et, iso-Pr, n-Bu, iso-Bu, iso-C₅H₁₁, PhCH₂, PhCH₂CH₂) in the presence of AlCl₃ to give α-silyl-α,β-unsaturated enones 3a-3h with high E stereoselectivity along with trans-α,β-unsaturated ketones 4a-4h. The enones 3 can be partially converted into the ketones 4 with an excess of AlCl₃. Reaction of 1 with RCOCl, (R = Ph, CH₃CH=CH) afforded only the ketones 4. Yields were dependent on time and the amounts of AlCl₃ used.

Full text of DOI:10.1016/j.jorganchem.2008.02.032

Journal of Organometallic Chemistry 693 (2008) 2004–2008
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Study of the reaction of 1,1-bis(trimethylsilyl)-2-phenylethylene with some acyl
chlorides in the presence of AlCl3
*
Kazem D. Safa , Soleiman Paymard Samani, Shahin Tofangdarzadeh, Akbar Hassanpour
Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz, 51664 Tabriz, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
1,1-Bis(trimethylsilyl)-2-phenylethylene (1), which has been synthesized from the Peterson reaction
between (Me3Si)3CLi and benzaldehyde, reacts with various acyl chlorides (RCOCl, R = Me, Et, iso-Pr,
n-Bu, iso-Bu, iso-C5H11, PhCH2, PhCH2CH2) in the presence of AlCl3 to give a-silyl-a,b-unsaturated enones
3a–3h with high E stereoselectivity along with trans-a,b-unsaturated ketones 4a–4h. The enones 3 can be
partially converted into the ketones 4 with an excess of AlCl3. Reaction of 1 with RCOCl, (R = Ph,
CH3CH=CH) afforded only the ketones 4. Yields were dependent on time and the amounts of AlCl3 used.
Ó 2008 Elsevier B.V. All rights reserved.
Received 30 January 2008
Received in revised form 27 February 2008
Accepted 29 February 2008
Available online 5 March 2008
Keywords:
Tris(trimethylsilyl)methane
Peterson olefination
1,1-Bis(trimethylsilyl)-2-phenylethylene
Friedel–Crafts reaction
1. Introduction
phenylethylene (1), with various readily available acyl chlorides.
This investigation led to a novel route for the synthesis of new a-
Vinylsilanes have recently found extensive use in organic syn-
thesis; notably their electrophilic chemistry has attracted atten-
tion. The addition of an electrophile to a vinylsilane results in the
build-up of electrophilic character b in the carbon–silicon bond
[1–5]. a-Silyl-a,b-unsaturated enones have become important for
the synthesis of a-halo-a,b-unsaturated ketones and their deriva-
tives. The preparation of a-silyl-a,b-unsaturated enones by Zr-
promoted ene-yne cyclization–carbonylation [6], Pd-catalyzed
acylation of a-silylalkenylmetals [7], and the Grignard reaction of
vinylsilanes with carbonyl compounds [8], have been studied.
However, these methods show poor selectivity and require
expensive reagents. Here, we present a convenient and stereoselec-
tive route for the synthesis of a-silyl-a,b-unsaturated enones
from 1,1-bis(trimethylsilyl)-2-phenylethylene. We have found that
the reaction is highly sensitive to time and the amount of AlCl3
used.
silyl-a,b-unsaturated enones. The precursor for our work was
tris(trimethylsilyl)methane, (Me3Si)3CH, prepared from the reac-
tion between CHCl3, Li and Me3SiCl in THF. The solvated organo-
lithium reagent, (Me3Si)3CLi, which was obtained by treatment of
(Me3Si)3CH with MeLi under reflux in THF [15], reacts with benzal-
dehyde in Et2O to give 1 (Scheme 1) [15,16].
Initially we studied the reaction of the bis(trimethylsilyl)alkene
1 with iso-butyryl chloride (2c) in the presence of AlCl3 in CH2Cl2
at 0 °C to give the related a-silyl-a,b-unsaturated enone 3c along
with the undesired a,b-unsaturated ketone 4c (Scheme 2). In order
to optimize conditions for the formation of 3c, we decided to
investigate the reaction of 2c (4 mmol) with various amounts of
AlCl3. When 18 mequiv. of AlCl3 was used with a reaction time
of 1 h, the major product was the a-silyl-a,b-unsaturated enone
3c, but it was the a,b-unsaturated ketone 4c when 36 mequiv. of
AlCl3 was used with a reaction time of 3 h. Table 1 shows that
the ratio of 4c/3c increased with prolongation of the reaction
time(from 60 min to 150 min). Moreover we found that when
the purified product 3c reacts with AlCl3 under the same condi-
tions, it is partially converted into 4c (Scheme 2). Consequently,
the present method can also provide a synthesis of a,b-unsatu-
rated ketones.
2. Results and discussion
The use of silicon-based reagents to accomplish carbon–carbon
bond-forming reactions is a part of our recent research on the
development of organosilicon reagents for synthesis [9–14]. We
decided to investigate the reaction of 1,1-bis-(trimethylsilyl)-2-
It has previously been shown that Friedel–Crafts reactions of
vinylsilanes often lead to both addition and substitution products
[17,18], but in the case of the bis(trimethylsilyl)alkene 1 because
of steric hindrance, only substitution products have been obtained.
* Corresponding author. Tel.: +98 411 3393124; fax: +98 411 3340191.
E-mail address: dsafa@tabrizu.ac.ir (K.D. Safa).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.02.032

K.D. Safa et al. / Journal of Organometallic Chemistry 693 (2008) 2004–2008
2005
Table 1
Ph
H
SiMe3
SiMe3
The effect of time and amount of AlCl3 on the reaction of 4 mmol 2c with 4 mmol 1
Et2O
+
(Me3Si)3CLi
PhCHO
Entry
1
Time (min)
30
AlCl3/RCOCl
3c (%)a
4c (%)a
Ratio 4c/3c
1.5
3
35
45
20
30
0.57
0.67
1
Scheme 1. Preparation of 1,1-bis(trimethylsilyl)-2-phenylethylene via Peterson
olefination.
2
3
4
5
a
60
1.5
3
62
50
30
45
0.48
0.9
90
1.5
3
55
45
40
50
0.73
1.1
The plausible mechanism for this reaction is depicted in Scheme 3.
The initial step is the coordination of the acyl chloride to the Lewis
acid to give complex 5, which can be served as an electrophile. The
carbocation intermediate 6 can be stabilized with Me3Si groups (Si
b-effect). Finally, it loses a SiMe3Cl to give an alkene 3.
Following our study on the synthesis of a-silyl-a,b-unsaturated
enones (3), the optimum conditions (Table 1, entry 2, AlCl3/
RCOCl = 1.5, 60 min and room temperature) have been used for
reactions with various acyl chlorides (RCOCl, R = Me, Et, Bu,
iso-Bu, n-C5H11, PhCH2, PhCH2CH2) to give the related a-silyl-a,
b-unsaturated enones 3a–3h along with the undesired a,b-unsatu-
rated ketones 4a–4h (Table 2).
120
180
1.5
3
49
40
47
57
0.96
1.43
1.5
3
38
30
58
68
1.53
2.27
Yields calculated by GC–mass spectrometry.
O
Ph
H
SiMe3
AlCl4-
C
Cl
O+
(5)
AlCl3
SiMe
+
R
+
R
SiMe3
As seen in Table 2, the reactions show high stereoselectivity
(higher than that reported for alternative methods [6–8]) to pro-
vide only E stereoisomers. The values of the chemical shifts and
3
coupling constants JHH of the vinylic protons show that all the
a,b-unsaturated ketones 4 reported here have trans stereochemis-
try. These results can be explained simply by considering the dif-
ferences in the size of the various groups that are attached to
C@C bonds. We also studied the reaction of 1 with benzoyl and
crotonyl chloride but all attempts to isolate a-silyl-a,b-unsaturated
enones were unsuccessful. Whatever the conditions, only 4i and 4j
were detected (Scheme 4).
Ph
3
O
Ph
COR
SiMe
Cl
+
+
Me3SiCl
H
Cl
SiMe
3
3
H
(3)
(6)
Scheme 3. Plausible mechanism for the preparation of a-silyl-a,b-unsaturated
enones.
3. Conclusion
Although several methods are available for the preparation of a-
silyl-a,b-unsaturated enones, we believe the present method offers
considerable advantages in terms of simplicity, high stereoselectiv-
ity and mild conditions. Moreover, we found that under suitable
conditions, this method provides a route to trans-a,b-unsaturated
ketones.
4.2. Spectra
The 1H NMR and 13C NMR were recorded with a Bruker FT-
400 MHz spectrometer at room temperature and CDCl3 as a sol-
vent. The mass spectra were obtained with a GC-Mass Agilent,
quadrupole mode 5973N instrument, operating at 70 eV. The FTIR
spectra were recorded on a Bruker-Tensor 270 spectrometer. Ele-
mental analyses were carried out with an Elementar vario EL III
instrument.
4. Experimental
4.1. Solvents and reagents
4.3. Preparation of tris(trimethylsilyl)methyllithium, (Me3Si)3CLi, in
THF
The reactions were carried out under dry argon. Solvents were
dried by standard methods. Substrates for the preparation of
tris(trimethylsilyl)methyllithium, viz. Me3SiCl (Merck), Li (Merck),
CHCl3 (Merck), and PhCOH (Merck) were used as received. All acyl
chlorides were purchased from Merck and distilled before use.
AlCl3 was used after sublimation.
The reagent was prepared as described by Eaborn and co-work-
ers [14] and consisted typically of a solution of 5 mmol (Me3Si)3CLi
in 25 ml of THF, with 4 ml of Et2O always present from the MeLi
used in its preparation.
Ph
H
SiMe3
H
Me3Si
(CH3)2HC
H
Ph
H
O
AlCl3
+
+
CH2Cl2
Cl
(CH3)2HC
SiMe3
(CH3)2HC
(2c)
Ph
O
O
(1)
(4c)
(3c)
AlCl3
Scheme 2. AlCl3 mediated reactions of 1 with iso-butyryl chloride.

2006
K.D. Safa et al. / Journal of Organometallic Chemistry 693 (2008) 2004–2008
1682 (C@O), 1580 (C@C); 1H NMR (400 MHz, CDCl3): d 2.37 (s, 3H,
CH3), 6.71 (d, 1H, J = 16 Hz, PhHC@CH), 7.38–7.59 (m, 6H,
PhHC@CH and Ar);13C NMR (CDCl3): d 26.5 (CH3), 126.1–142.4
(Ph and C@C), 197.4 (C@O).
Table 2
The Friedel–Crafts reaction of 4 mmol 1 with 4 mmol 2b–2h in the presence of
18 mequiv.a AlCl3(AlCl3/RCOCl = 1.5) during 60 minb
Ph
H
Me3Si
R
SiMe3
SiMe3
AlCl3
O
H
H
Ph
H
+
4.4.2. Reaction of 1 with C2H5COCl (2b)
R
Cl
+
CH2Cl2
R
Ph
From the reaction of propionyl chloride (0.38 g) with
1
O
O
(1.00 g, 4.03 mmol) TLC on silica gel (4:1 n-hexane:diethyl ether)
gave products 3c (Rf = 0.54) and 4c (Rf = 0.27, m.p. 38 °C). 3c:
FTIR (KBr, cmÀ1): 3062 (Ar–H), 1676 (C@O), 1676, 1491 (Ph),
1598 (C@C), 1251, 843 (Si–CH3); 1H NMR (400 MHz, CDCl3): d
(1)
(2)
(3)
(4)
3
0.22 (s, 9H, Si(CH3)3), 0.97 (t, 3H, JHH = 7 Hz, CH3), 2.25–2.30
3(%)b
4(%)
(q, 2H, CH2), 6.82 (s, 1H, vinyl), 7.24–7.31 (m, 5H, Ar); 13C
NMR (CDCl3): d À2.5 (Si(CH3)3), 7.0 (CH3), 35.4 (CH2), 127.3–
149.2 (Ph, C@C), 212.16 (C@O); m/z (EI): 218 (11%, [MÀMe]+),
203 (100%, [MÀEt]+), 128 (11%, [PhC@CCO]+), 73 (33%,
[Si(CH3)3]+). Anal. Calc. for C14H20SiO: C, 72.4; H, 8.6. Found: C,
72.3; H, 8.6%. 4c: FTIR (KBr, cmÀ1): 3032 (Ar–H), 1681 (C@O),
1613, 1490 (Ph); 1H NMR (400 MHz, CDCl3): d 1.17 (t, 3H,
3JHH = 7 Hz, CH3), 2.67–2.71 (q, 2H, CH2), 6.75 (d, 1H,
3JHH = 16 Hz, PhHC@CH), 7.37–7.58 (m, 6H, PhHC@CH and Ar);
13C NMR (CDCl3): d 7.2 (CH3), 33.0 (CH2), 125.0–141.2 (Ph,
C@C), 199.9 (C@O).
RCOCl
R
E
Z
2a
2b
2c
2d
2e
2f
Me
Et
61
50
62
53
61
60
50
58
–
–
–
3
–
4
–
–
30
20
30
42
38
31
20
15
iso-Pr
iso-But
n-But
n-Pen
Ph-CH2
Ph-CH2–CH2
2g
2h
a
mequiv. means milliequivalent.
As explained in text, this condition was the optimized condition for preparation
b
of 3.
4.5.3. Reaction of 1 with iso-C3H7 (2c)
From the reaction of 2a (0.43 g) with 1(1.00 g, 4.03 mmol) li-
quid products 3a (Rf = 0.54) and 4a (Rf = 0.27) were obtained by
TLC on silica gel (4:1 n-hexane:diethyl ether). 3c: FTIR (KBr,
cmÀ1): 3139 (Ar–H), 1670 (C@O), 1670, 1457 (Ph), 1581 (C@C),
1251, 842 (Si–CH3); 1H NMR (400 MHz, CDCl3): d 0.35 (s, 9H,
Ph
H
H
PhCOCl
AlCl3
(4i)
O
55%
Ph
Ph
H
SiMe3
SiMe3
O
CH2Cl2
3
Si(Me3)3), 1.08 (d, 6H, JHH = 7 Hz, CHC(CH3)2), 2.49–2.60 (m, 1H,
O
CH(CH3)3), 7.08 (s, 1H, vinyl), 7.33–7.46 (m, 5H, Ar); 13C NMR
AlCl3
CH2Cl2
(CDCl3):
d
À1.9 (Si(CH3)3), 17.6 (CH(CH3)2), 39.7 (CH(CH3)2),
CH3CH=CHCOCl
cis and trans
127.0–148.7 (Ph, C@C), 214.9 (C@O); m/z (EI): 231 (6%, [MÀCH3]+),
203 (100%, [MÀCH(CH3)2]+), 129 (6%, [PhC@CCO]+), 73 (41%,
[Si(CH3)3]+). Anal. Calc. for C15H22SiO: C, 73.1; H, 8.9. Found: C,
73.2; H, 8.5%.
+
(4j)
Ph
Ph
cis - trans
7%
trans - trans
81%
4a: FTIR (KBr, cmÀ1): 3031 (Ar–H), 1680 (C@O), 1612, 1457
Scheme 4. Reaction of 1 with benzoyl and crotonyl chloride in the presence of
(Ph); 1H NMR (400 MHz, CDCl3): d 1.19 (d, 6H, JHH = 7 Hz,
3
AlCl3.
CHC(CH3)2), 2.89–2.98 (m, 1H, CH(CH3)2), 6.82 (d, 1H, 3JHH = 16 Hz,
PhHC@CH), 7.38–7.63 (m, 6H, PhHC@CH and Ar); 13C NMR (CDCl3):
d 17.5 (CH(CH3)2), 38.3 (CH(CH3)2), 123.4–141.4 (Ph, C@C), 202.79
(C@O).
4.4. General procedure
A solution of 1,1-bis(trimethylsilyl)-2-phenylethylene (1) [16]
(1.00 g, 4.03 mmol) in dry CH2Cl2 (20 ml) was added during
15 min at 0 °C under argon to a stirred solution of anhydrous alu-
minum trichloride (0.8 g, 18 mequiv.) in dry CH2Cl2 (30 ml) con-
taining acyl chloride (4.03 mmol), and the mixture was stirred at
0 °C for a further 45 min. The reaction was added to water
(50 ml) then the organic layer was separated and the aqueous layer
was extracted twice with 50 ml Et2O. The combined extracts were
dried over anhydrous sodium sulfate and filtered. The solvent was
evaporated from the filtrate and the residue separated by prepara-
tive TLC (silica gel) to give the products.
4.5.4. Reaction of 1 with C4H9COCl (2d)
The reaction of 2d (0.49 g) with 1 (1.00 g, 4.03 mmol) followed
by TLC on silica gel (8:1 n-hexane:diethyl ether) gave products 3d
(Rf = 0.54) and 4d (Rf = 0.27, m.p. 34–36 °C). 3d: FTIR (KBr, cmÀ1):
3062, 3018 (Ar–H), 1674 (C@O), 1597, 1482 (Ph), 1251, 843 (Si–
CH3); 1H NMR (400 MHz, CDCl3): d 0.21 (s, 9H, SiMe3), 0.78 (t,
3
3H, JHH = 4 Hz, CH3), 1.19–1.23 (m, 2H, CH2–CH3), 1.44–1.52 (q,
3
2H, CH2–CH2–CH3), 2.26 (t, 2H, JHH = 7 Hz, CO–CH2), 6.82 (s, 1H,
PhHC@C), 7.22–7.34 (m, 5H, Ar); 13C NMR (CDCl3):
d
À2.5
(Si(CH3)3), 12.8 (CH3), 21.0 (CH2–CH3), 24.7 (CH2–CH2–CH3), 41.8
(CO–CH2), 127.3–149.3 (Ph, C@C), 211.5 (C@O); m/z (EI): 260
(5%, [M]+), 245 (7.6%, [MÀMe]+), 203 (100%, [MÀ(CH2)3CH3]+),
128 (7%, [PhC@CCO]+), 73 (38%, [Si(CH3)3]+). Anal. Calc. for
4.4.1. Reaction of 1 with CH3COCl (2a)
For the reaction with 2b (0.32 g). TLC on silica gel (8:1 n-hex-
ane:diethyl ether as eluant) gave 3b (Rf = 0.60) and 4b (Rf = 0.30,
m.p. 39 °C). 3b: FTIR (KBr, cmÀ1): 3062 (Ar–H), 1676 (C@O),
1676, 1491 (Ph), 1587 (C@C), 1252, 843 (Si–CH3); 1H NMR
(400 MHz, CDCl3): d 0.23 (s, 9H, SiMe3), 2.06 (s, 3H, CH3), 6.80 (s,
1H, vinyl), 7.28–7.30 (m, 5H, Ar); 13C NMR (CDCl3): d À2.6 (SiMe3),
30.1 (CH3), 127.0–149.3 (Ph and C@C), 209.6 (C@O); m/z (EI): 218
(35%, [M]+), 203 (100%, [MÀMe]+), 145 (6%, [MÀSiMe3]+), 129 (41%,
[PhC@CCO]+), 73 (40%, [SiMe3]+). Anal. Calc. for C13H18SiO: C, 71.5;
H, 8.2. Found: C, 71.9; H, 8.5%. 4b: FTIR (KBr, cmÀ1): 3033 (Ar–H),
C
16H24SiO: C, 73.8; H, 9.2. Found: C, 73.5; H, 9.0%. 4d: FTIR (KBr,
cmÀ1): 3049, 3025 (Ar–H), 1653 (C@O), 1653, 1495 (Ph); 1H NMR
3
(400 MHz, CDCl3): d 0.94 (t, 3H, JHH = 7 Hz, CH3), 1.33–1.43 (m,
2H, CH2-CH2–CH3), 1.62–1.70 (q, 2H, CH2–CH2–CH3), 2.66 (t, 2H,
3JHH = 8 Hz, CO–CH2–CH2), 6.73 (d, 1H, JHH = 16 Hz, PhHC@CH),
3
7.36–7.56(m, 6H, PhHC@CH, Ar); 13C NMR (CDCl3): d 12.8 (CH3),
21.4 (CH2–CH3), 25.4 (CH2–CH2–CH3), 39.6 (CO–CH2), 125.1–
141.2 (Ph, C@C), 199.6 (C@O).

K.D. Safa et al. / Journal of Organometallic Chemistry 693 (2008) 2004–2008
2007
4.5.5. Reaction of 1 with iso-C4H9COCl (2e)
1679, 1493 (Ph), 1252, 843 (Si–CH3); 1H NMR (400 MHz, CDCl3):
3
The reaction between 2e (0.49 g) and 1 (1.00 g, 4.03 mmol) gave
liquid products 3e (Rf = 0.54) and 4e (Rf = 0.27), separated by TLC
on silica gel (8:1 n-hexane:diethylether). 3e: FTIR (KBr, cmÀ1):
3062, 3020 (C–H Ar), 1674 (C@O), 1674, 1458 (Ph), 1251,842
(Si–CH3);1H NMR (400 MHz, CDCl3): d 0.22 (s, 9H, Si(CH3)3), 0.81
d 0.13 (s, 9H, Si(CH3)3), 2.54 (t, 2H, JHH = 7 Hz, CH2CH2Ph), 3.55
3
(t, 2H, JHH = 7 Hz, CH2CH2Ph), 6.97 (s, 1H, vinyl), 7.01–7.36 (m,
10H, Ar); 13C NMR (CDCl3): d À2.6 (Si(CH3)3), 29.1 (CH2Ph), 41.4
(CH2CH2Ph), 125.1–141.7 (Ph, C@C), 198.3 (C@O); m/z (EI): 307
(7.7%, [MÀ1]+), 231 (100%, [MÀPh]+), 158 (55%, [PhHC@
CCOCH2CH2]+), 73 (84%, [SiMe3]+). Anal Calc. for C20H24SiO: C,
77.9; H, 7.7. Found: C, 77.9; H, 7.7%. 4h: FTIR (KBr, cmÀ1): 3065,
3036 (Ar–H), 1712 (C@O), 1602, 1465 (Ph);1H NMR (400 MHz,
CDCl3): 2.67 (t, 2H, 3JHH = 7 Hz, CH2CH2Ph), 3.13 (t, 2H, 3JHH = 7 Hz,
3
(d, H, JHH = 6 Hz, CH(CH3)2), 2.06–2.12 (m, 1H, CH2CH(CH3)2),
3
2.17 (d, 2H, JHH = 6 Hz, COCH2CH(CH3)2), 6.81 (s, 1H, PhHC@C),
7.23–7.35 (m, 5H, Ar); 13C NMR (CDCl3): d À2.4 (Si(CH3)3), 21.6
(CH(CH3)2), 22.3 (CH(CH3)2), 50.6 (CH2CH(CH3)2), 127.3–149.3
(Ph, C@C), 210.5 (C@O); m/z (EI): 260 (23%, [M]+), 245 (69%,
[MÀMe]+), 218 (38%,[MÀCH(CH3)2]+), 203 (100%, [MÀCH2CH-
(CH3)2]+), 128 (20%, [PhC@CCO]+), 73 (92%, [SiMe3]+). Anal. Calc.
for C16H24SiO: C, 73.8; H, 9.2. Found: 73.6; H, 8.9%. 4e: FTIR (KBr,
cmÀ1): 3032 (C–H Ar), 1682(C@O), 1659, 1494 (Ph); 1H NMR
3
CH2CH2Ph), 6.79 (d, 1H, JHH = 16 Hz, PhHC@CH), 7.27–7.53 (m,
3
10H, Ar), 7.63 (d, 1H, JHH = 16 Hz, PhHC@CH); 13C NMR (CDCl3):
d 24.7 (CH2Ph), 35.1 (CH2CH2Ph), 124.1–149.3 (Ph, C@C), 196.2
(C@O).
3
(400 MHz, CDCl3): d 0.98 (d, 6H, JHH = 7 Hz, CH(CH3)2), 2.20–2.27
4.5.9. Reaction of 1 with benzoyl chloride (2i)
3
(m, 1H, CH2CH(CH3)2), 2.53 (d, 2H, JHH = 7 Hz, CH2CH(CH3)2),
The reaction of 2i (0.56 g) with 1 (1.00 g, 4.03 mmol) gave a sin-
gle solid product 4i (m.p. 56–57 °C) isolated by preparative TLC
(silica gel; 3:2 n-hexane:diethyl ether, Rf = 0.4), FTIR (KBr, cmÀ1):
3060 (Ar–H), 1661 (C@O), 1605, 1495 (Ph);1H NMR (400 MHz,
CDCl3): d 7.39–8.04 (m, 12H, Ar and vinyl); 13C NMR (CDCl3): d
121.1–143.8 (Ph, C@C), 191.1 (C@O).
3
6.73 (d, 1H, JHH = 16 Hz, PhHC@CH), 7.37–7.56 (m, 6H, PhHC@CH,
Ar); 13C NMR (CDCl3): d 21.6 (CH(CH3)2), 24.1 (CH(CH3)2), 48.8
(CH2CH(CH3)2), 125.5–141.3 (Ph, C@C), 199.3 (C@O).
4.5.6. Reaction of 1 with C5H11COCl (2f)
The reaction of 1(1.00 g, 4.03 mmol) with 0.54 g of 2f followed
by TLC on silica gel (4:1 n-hexane:diethyl ether) gave products 3f
(Rf = 0.54) and 4f (Rf = 0.27, m.p. 36–38 °C). 3f: FTIR (KBr, cmÀ1):
3054 (Ar–H), 1657 (C@O), 1650, 1490 (Ph), 1251, 843 (Si–CH3);
1H NMR (400 MHz, CDCl3): d 0.21 (s, 9H, Si(CH3)3), 0.81 (t, 3H,
3JHH = 7 Hz, CH2CH3), 1.11–1.22 (m, 4H, CH2CH2CH3), 1.46–1.53
4.5.10. Reaction of 1 with PhCH2CH2COCl (2j)
To a stirred mixture of 2j (0.42 g) and AlCl3 (0.8 g) was added
drop wise 1 (1.00 g, 4.03 mmol) according to the general procedure
A yellow product 4j was obtained by TLC (silica gel; 4:1 n-hex-
ane:diethyl ether, Rf = 0.6). FTIR (KBr, cmÀ1): 3031 (Ar–H), 1666
(C@O), 1624, 1494 (Ph), 1605(C@C);1H NMR (400 MHz, CDCl3): d
3
(q, 2H, COCH2CH2CH2), 2.25 (t, 2H, JHH = 8 Hz, COCH2CH2), 6.816
(s, 1H, vinyl), 7.24–7.30 (m, 5H, Ar); 13C NMR (CDCl3): d À2.5
(Si(CH3)3), 12.8 (CH2CH3), 21.3 (CH2–CH3), 30.1 (CH2–CH2–CH3),
42.0 (COCH2CH2), 52.4 (CO–CH2), 127.0–149.3 (Ph, C@C), 211.6
(C@O); m/z (EI): 274 (5%, [M]+), 259 (8%, [MÀMe]+), 218 (6%,
[MÀ(CH2)3CH3]+), 203 (100%, [MÀ(CH2)4CH3]+), 73 (30%, [SiMe3]+).
Anal. Calc. for C17H26SiO: C, 74.4; H, 9.4. Found: C, 74.8; H, 9.0%.
4f: FTIR (KBr, cmÀ1): 3054, 3024 (Ar–H), 1657 (C@O), 1657,
1.96–1.98 (dd, 3H, JHH = 7, 1 Hz, CH3), 6.44–6.49 (qq, 1H,
3
3
3JHH = 16 Hz, CH3HC@CH), 6.97 (d, 1H, JHH = 16 Hz, PhHC@CH),
6.98–7.07 (m, 1H, CH3HC@CH), 7.37–7.59 (m, 5H, Ph), 7.63(d, 1H,
3JHH = 16 Hz, PhHC@CH); 13C NMR (CDCl3): d 17.4 (CH3), 123.7–
142.4 (Ph, C@C), 188.1 (C@O). GC–mass spectrometric analysis of
the crude product indicated that both trans–trans and cis–trans ste-
reoisomer were formed, but only trans–trans isomer was isolated
by TLC.
3
1496 (Ph); 1H NMR (400 MHz, CDCl3): d 0.90 (t, 3H, JHH = 7 Hz,
CH2CH3), 1.31–1.38 (m, 4H, CH2CH2CH3), 1.65–1.72 (q, 2H,
3
COCH2CH2CH2), 2.66 (t, 2H, JHH = 8 Hz, COCH2CH2), 6.74 (d, 1H,
Acknowledgement
3JHH = 16 Hz, PhHC@C), 7.37–7.57 (m, 6H, PhHC@CH, Ar); 13C
NMR (CDCl3): d 12.9 (CH3), 21.5 (CH2–CH3), 23.0 (CH2–CH2–CH3),
30.5 (COCH2CH2), 39.9 (CO–CH2), 125.2–141.2 (Ph, C@C), 199.7
(C@O).
We thank Dr. J. D. Smith for his helpful comments.
References
4.5.7. Reaction of 1 with PhCH2COCl (2g)
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The reaction 1 (1.00 g, 4.03 mmol) with 2g (0.62 g) followed by
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(Rf = 0.6) and 4g (Rf = 0.3, m.p. 68–71 °C). Spectroscopic data for
3g: FTIR (KBr, cmÀ1): 3063, 3029 (Ar–H), 1677 (C@O), 1677,
1493 (Ph), 1254, 843 (Si–Me3); 1H NMR (400 MHz, CDCl3): d
0.12 (s, 9H, Si(CH3)3), 3.55 (s, 2H, CH2), 6.96 (s, 1H, vinyl), 7.01–
7.37 (m, 10H, Ar); 13C NMR (CDCl3): d À2.6 (Si(CH3)3), 49.1
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3JHH = 16 Hz, PhHC@CH), 7.27–7.53 (m, 10H, Ar), 7.64 (d, 1H,
3JHH = 16 Hz, PhHC@CH); 13C NMR (CDCl3): d 47.37 (CH2), 124.1–
149.4 (Ph, C@C), 196.3 (C@O).
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4.5.8. Reaction of 1 with PhCH2CH2Cl (2h)
The reaction of 2h (0.68 g) with 1 (1.00 g, 4.03 mmol) gave after
TLC on silica gel (3:2 n-hexane:diethyl ether) 3h (Rf = 0.6) and 4h
(Rf = 0.35). 3h: FTIR (KBr, cmÀ1): 3063, 3029 (Ar–H), 1679 (C@O),

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1
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