Stereoselective preparation of (Z)-γ-silyl-γ,δ-unsaturated ketones and their application in the synthesis of 1,4-Diketones

Article abstract of DOI:10.1055/s-2002-35624

Hydrozirconation reaction of alkynylsilanes 1 followed by Michael addition to α,β-unsaturated ketones in the presence of CuBr Me₂S complex produced (Z)-γ-silyl-γ,δ-unsaturated ketones 3 stereoselectively. 1,4-Diketones were prepared via epoxidation and hydrolysis of 3.

Full text of DOI:10.1055/s-2002-35624

PAPER
2497
Stereoselective Preparation of (Z)- -Silyl- , -Unsaturated Ketones and their
Application in the Synthesis of 1,4-Diketones
(Z)- -Silyl-
,
-Unsatura
e
ted Ketones
i
and th
x
eir Application in t
n
he Synthesis of 1,4
Z
-Diketones heng,a Xian Huang*a,b
a
Department of Chemistry, Zhejiang University (Xixi Campus, Hangzhou 310028, P. R. China
b
The State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
P. R. China
E-mail: huangx@mail.hz.zj.cn
Received 12 July 2002; revised 9 September 2002
ketones in the presence of copper (I) reagent and their util-
ity in the synthesis of 1,4-diketones via epoxidation and
hydrolysis.
Abstract: Hydrozirconation reaction of alkynylsilanes 1 followed
by Michael addition to , -unsaturated ketones in the presence of
CuBr Me2S complex produced (Z)- -silyl- , -unsaturated ketones
3 stereoselectively. 1,4-Diketones were prepared via epoxidation
and hydrolysis of 3.
Hydrozirconation of 1-alkynylsilanes 1 at room tempera-
ture in THF gave (E)- -zirconated vinyl silanes 2, which
reacted conjugatively with , -unsaturated ketones in the
presence of 15 mol% CuBr Me2S at 25 °C to yield (Z)- -
silyl- , -unsaturated ketones 3 predominately in moder-
ate to good yields (Scheme 1). The results are listed in
Table 1.
Key words: silicon, zirconium, Michael additions, ketones,
enones, alkynes
Alkenylsilanes serve as important intermediates in organ-
ic synthesis.1 It is well documented that the -silyl- , -un-
saturated ketones are essentially used in the synthesis of
jasmone.2 However, only a few synthetic methods for -
silyl- , -unsaturated ketones have been published,3,4
which had the disadvantage of low stereoselectivity.3 In
our preliminary work, the bifunctional ethenyl reagent
containing silyl and zirconium moieties was obtained by
the hydrozirconation reaction of alkynylsilanes.5 Based
on the high reactivity of the zirconium group, the electro-
philic substitution to the zirconated intermediate could
produce the polysubstituted vinyl silanes with high regio-
and stereoselectivity. Owing to the silyl group, the vinyl
silanes also have great potential to be converted to some
useful compounds.
Scheme 1
On the other hand, 1,4-diketones are widely used as build-
ing blocks for the preparation of five-membered
carbocyclic and heterocyclic compounds.6A number of
methods for the synthesis of 1,4-diketones have been de-
veloped.7–10 Among them, the Michael–Stetter addition of
aldehydes to , -unsaturated ketones,7 cross aldol con-
densation of methyl ketones with -bromo ketones fol-
lowed by 1,3-dehydrobromination of the products and
cleavage of cyclopropyl intermediates,8 the alkylation of
stabilized alkaline metal enolates,9 enamines,9b and tin
enolates10 by -halocarbonyl compounds are mainly de-
scribed. Also, the conjugate acylation of an enone by an
acyl anion equivalent is a very important process. Devel-
oping acyl anion equivalents and the resulting polarity
umpolung of carbon atoms remain challenging problems.
1
The investigation of H NMR spectra of the crude prod-
ucts showed the purity of Z-isomer was above 88%. When
R was phenyl in compound 3 (Entry 1–5 in Table 1), the
Z-configuration was verified by the X-ray diffraction
study of compound 3d (Figure 1).11 It could be observed
that the syn-addition of Cp2Zr(H)Cl to phenylacetylenic
silane led the zirconium atom occupying the carbon adja-
cent to the silyl group.
For compounds 3f–o as oils, 1H NMR spectroscopy
showed that the olefinic proton signal was characteristi-
Herein, we wish to report the synthesis of (Z)- -silyl , -
unsaturated ketones by hydrozirconation of alkynyl si-
lanes followed by conjugate reaction to , -unsaturated
Synthesis 2002, No. 17, Print: 02 12 2002.
Art Id.1437-210X,E;2002,0,17,2497,2502,ftx,en;F05602SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881
Figure 1 ORTEP drawing of compound 3d.

2498
W. Zheng, X. Huang
PAPER
Table 1 Synthesis of -Silynyl , -Unsaturated Ketones 3
Entry
R
R1
R2
Producta
Reaction conditions:
Temp (°C)/time (h)
Yield (%)b
(3/3 )c
1
2
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
25/4
25/4
25/5
25/5.5
25/5
25/1.5
25/2.5
25/3
25/3
25/4
25/2
25/2
25/3
25/3
25/4
63 (96/4)
66 (95/5)
68 (95/5)
70 (93/7)
66 (95/5)
76 (90/10)
83 (90/10)
56 (88/12)
66 (89/11)
60 (90/10)
72 (91/9)
80 (92/8)
54 (92/8)
59 (93/7)
60 (92/8)
Ph
Ph
p-CH3OC6H4
m-NO2C6H4
CH3
3
Ph
Ph
4
Ph
p-NO2C6H4
(CH2)3
Ph
5
Ph
6
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C5H11
n-C5H11
n-C5H11
n-C5H11
n-C5H11
Ph
7
Ph
p-CH3OC6H4
m-NO2C6H4
CH3
3g
3h
3i
8
Ph
9
p-NO2C6H4
(CH2)3
Ph
10
11
12
13
14
15
3j
Ph
3k
3l
Ph
p-CH3OC6H4
m-NO2C6H4
CH3
Ph
3m
3n
3o
p-NO2C6H4
(CH2)3
a All products were identified by 1H NMR, IR, MS and elemental analyses.
b Isolated yield of purified 3 was based on the alkynylsilanes used.
c Percent ratio of 3/3 was determined by the integral value of the vinylic protons in the 1H NMR spectra of the crude products.
cally split into a triplet with coupling constant 3J procedures, mild reaction conditions and good yields. The
(H,H) = 7.2 Hz, which indicated the zirconium moiety oc- polarity umpolung of the -silyl vinylic carbon atom oc-
cupied the -position carbon atom of the silyl group, curred in the synthesis of 1,4-diketones 5, and the inter-
which exhibited the same regioselectivity as that of the mediate of the hydrozirconation reaction of alkynylsilane,
1
3d. The Z-olefin geometry was affirmed by H–1H 2D (E)- -zirconated vinyl silane, served as an acyl anion
NOSEY spectra of 3l (Figure 2).
equivalent (Scheme 3).13 The investigation on the applica-
tion of (Z)- -silyl , -unsaturated ketones in organic syn-
thesis is still in progress.
Figure 2 The 1H–1H 2D NOESY correlation of compound 3l.
Scheme 2
Epoxidation of 3 with m-chloroperbenzoic acid occurred
at the vinyl silanes to give epoxides 4, which were treated
with trifluoroacetic acid in refluxing methanol to afford 5
in good yields12 (Scheme 2 and Table 2).
O
R
SiMe3
R
ZrCp2
Cl
In conclusion, we have developed a novel route to the syn-
thesis of (Z)- -silyl , -unsaturated ketones and studied
their application in the synthesis of 1,4-diketones, which
has the advantages of readily available materials, simple
Scheme 3
Synthesis 2002, No. 17, 2497–2502 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
(Z)-γ-Silyl-γ,δ-Unsaturated Ketones and their Application in the Synthesis of 1,4-Diketones
2499
(Z)-1-(4 -Methoxylphenyl)-3,5-diphenyl-4-trimethylsilyl-4-
Table 2 Synthesis of 1,4-Diketones 5
penten-1-one (3b)
Yield: 66%; pale yellow oil.
Entry
R
R1
R2
Producta Yield (%)b
IR (neat): 2955, 1676, 1600, 1510, 1492, 1257, 1218, 1169, 837,
734 cm–1.
1H NMR (400 MHz, CDCl3): = –0.01 (s, 9 H), ABX, A = 3.17,
B = 3.76, X = 5.09 (JAX = 5.6 Hz, JBX = 8.8 Hz, JAB = 16.4 Hz, 3
H), 3.86 (s, 3 H), 6.83 (d, J = 8.8 Hz, 2 H), 6.99 (s, 1 H), 7.17–7.31
(m, 10 H), 7.79 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 0.56, 42.64, 42.76, 55.60, 114.43,
127.88, 128.13, 128.31, 128.53, 128.73, 128.81, 131.92, 145.19,
159.66, 197.01.
1
2
3
4
5
6
7
Ph
Ph
Ph
5a
5b
5c
5d
5e
5f
81
84
69
80
85
88
75
Ph
Ph
p-CH3OC6H4
Ph
(CH2)3
Ph
C4H9
C4H9
C5H11
C5H11
Ph
(CH2)3
Ph
Ph
MS (EI): m/z (%) = 414 (M+, 5), 73 (100).
Ph
p-CH3OC6H4
5g
Anal. Calcd for C27H30O2Si: C, 78.22; H, 7.29. Found: C, 78.18; H,
7.26.
a All products were identified by 1H NMR, IR, MS or elemental anal-
yses.
b Isolated yield based of the (Z)- -silyl , -ketones used.
(Z)-3,5-Diphenyl-(3 -nitrophenyl)-4-trimethylsiyl-4-penten-1-
one (3c)
Yield: 68%; colorless crystals; mp 113–113.5°C (hexane).
IR (KBr): 3026, 2954, 1694, 1613, 1532, 1350, 1203, 838 cm–1.
1
The mps were uncorrected. H NMR spectra were recorded on a
Bruker Avance 400 (400 Hz) spectrometer in CDCl3 with TMS as
the internal standard; chemical shifts are quoted in ppm and J values
are given in Hz. IR spectra were recorded on a Bruker Vector 22
spectrometer. EIMS was run on a HP 5989B mass spectrometer.
Alkynyl silane,14 1,3-diphenyl 2-propen-1-one,15 1-(4 -meth-
oxyphenyl)-3-phenyl-2-propen-1-one,15 1-(3 -nitrophenyl)-3-phe-
1H NMR (400 MHz, CDCl3): = 0.01 (s, 9 H), ABX, A = 3.30,
B = 3.73, X = 5.08 (JAX = 7.6 Hz, JBX = 6.0 Hz, JAB = 16.0 Hz, 3
H), 7.00 (s, 1 H), 7.11–7.31 (m, 10 H), 7.49 (t, J = 8.0 Hz, 1 H), 7.99
(d, J = 7.6 Hz, 1 H), 8.28 (d, J = 7.6 Hz, 1 H), 8.50 (s, 1 H).
13C NMR (100 MHz, CDCl3): = 0.54, 41.04, 43.14, 122.93,
126.53, 126.91, 127.04, 127.62, 128.10, 128.21, 128.46, 129.61,
133.42, 137.83, 138.12, 140.13, 141.99, 146.03, 148.30, 196.46.
nyl
2-propen-1-one,15
4-(4 -nitrophenyl)-3-buten-2-one,16
CuBr Me2S,17 and Schwartz’s reagent [Cp2Zr(H)Cl]18 were pre-
pared according to the literature procedures. 2-Cyclohexen-1-one,
MCPBA, TFA, MeOH (AR), CH2Cl2 (AR) were obtained commer-
cially and used in reactions without any further purification. Petro-
leum ether with a bp 30–60 °C was used. THF was dried over
sodium benzophenone ketyl and freshly distilled before use.
MS (EI): m/z (%) = 429 (M+, 4), 73 (100).
Anal. Calcd for C26H27NO3Si: C, 72.69; H, 6.34. Found: C, 72.67;
H, 6.37.
(Z)-[4-(4 -Nitrophenyl)]-6-phenyl-5-trimethylsilyl-5-hexen-2-
one (3d)
Yield: 70%; colorless crystals; mp 82.5–83 °C (hexane).
IR (KBr): 2954, 1718, 1519, 1491, 1346, 1249, 840 cm–1.
1H NMR (400 MHz, CDCl3): = –0.20 (s, 9 H), 2.13 (s, 3 H), ABX,
(Z)- -Silyl , -Unsaturated Ketones 3a–o; General Procedure
To a suspension of Cp2Zr(H)Cl (2 mmol) in THF (5 mL) in a
Schlenk reaction tube, an alkynyl silane (1.0 mmol) was injected
under nitrogen. The mixture was stirred at r.t. until a clear pale yel-
low solution of alkenylsilanes 2 was obtained.
A = 2.93, B = 3.11, X = 4.44 (JAX = 8.3 Hz, JBX = 6.3 Hz,
To this pale yellow solution of 2, , -unsaturated ketone (1.2 mmol)
and CuBr Me2S (0.15 mmol) were added under nitrogen and the
mixture was stirred under the conditions listed in Table 1. The reac-
tion was quenched by sat. aq NH4Cl and extracted with Et2O. The
combined organic phase was dried (MgSO4) and evaporated. A pure
product was obtained by column chromatography (silica gel; pe-
troleum ether–EtOAc, 40:1).
JAB = 16.9 Hz, 3 H), 7.16 (d, J = 7.0 Hz, 2 H), 7.18–7.33 (m, 4 H),
7.47 (d, J = 8.7 Hz, 2 H), 8.17 (d, J = 8.7 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 0.08, 30.82, 45.13, 49.56, 123.76,
127.43, 128.06, 128.54, 129.45, 139.82, 142.02, 145.32, 146.72,
151.51, 206.04.
MS (EI): m/z (%) = 367 (M+, 3), 73 (100).
Anal. Calcd for C21H25NO3Si: C, 68.63; H, 6.86. Found: C, 68.60;
H, 6.84.
(Z)-1,3,5-Triphenyl-4-trimethylsilyl-4-penten-1-one (3a)
Yield: 63%; pale yellow oil.
IR (neat): 3025, 2953, 1687, 1448, 1249, 755, 699 cm–1.
(Z)-1-(Cyclohexanon-3-yl)-2-phenyl-1-trimethylethene (3e)
1H NMR (400 MHz, CDCl3): = 0.02 (s, 9 H), ABX, A = 3.25,
B = 3.83, X = 5.12 (JAX = 5.6 Hz, JBX = 8.9 Hz, JAB = 16.8 Hz, 3
H), 7.01 (s, 1 H), 7.16–7.52 (m, 13 H), 7.82–7.83 (m, 2 H).
13C NMR (100 MHz, CDCl3): = 0.70, 40.87, 42.64, 126.19,
126.92, 127.83, 128.11, 128.28, 128.38, 128.39, 128.61, 128.72,
132.96, 138.43, 139.72, 142.56, 147.01, 198.31.
Yield: 66%; colorless crystals; mp 46–47 °C (hexane).
IR (neat): 2952, 1713, 1446, 1250, 837 cm–1.
1H NMR (400 MHz, CDCl3): = –0.08 (s, 9 H), 1.56–1.67 (m, 2 H),
2.00–2.03 (m, 1 H), 2.10–2.13 (m, 1 H), 2.32–2.48 (m, 4 H), 2.64–
2.67 (m, 1 H), 7.14–7.31 (m, 6 H).
13C NMR (100 MHz, CDCl3): = 0.65, 25.58, 32.60, 41.40, 43.80,
48.54, 127.04, 127.90, 128.64, 140.26, 212.09.
MS (EI): m/z (%) = 384 (M+, 4), 73 (100).
MS (EI): m/z (%) = 272 (M+, 24), 73 (100).
Anal. Calcd for C26H28OSi: C, 81.20; H, 7.34. Found: C, 81.16, H,
7.39.
Anal. Calcd for C17H24OSi: C, 74.94; H, 8.88. Found: C, 74.98; H,
8.94.
Synthesis 2002, No. 17, 2497–2502 ISSN 0039-7881 © Thieme Stuttgart · New York

2500
W. Zheng, X. Huang
PAPER
(Z)-1,3-Diphenyl-4-trimethylsilyl-4-nonen-1-one (3f)
Yield: 76%; colorless oil.
Anal. Cald for C19H29NO3Si: C, 65.67; H, 8.41. Found: C, 65.69; H,
8.46.
IR (neat): 3061, 2956, 1599, 1248, 752 cm–1.
(Z)-1-(Cyclohexanon-3-yl)-1-trimethylsilyl-1-hexene (3j)
Yield: 60%; colorless oil.
IR (neat): 2956, 2861, 1715, 1447, 1249, 837, 758 cm–1.
1H NMR (400 MHz, CDCl3): = 0.14 (s, 9 H), 0.90 (t, J = 6.9 Hz,
3 H), 1.31–1.34 (m, 4 H), 1.36–1.48 (m, 1 H), 1.56–1.68 (m, 1 H),
1.76–1.86 (m, 1 H), 2.00–3.16 (m, 3 H), 2.26–2.42 (m, 5 H), 5.96 (t,
J = 7.4 Hz, 1 H).
13C NMR (100 MHz, CDCl3): = –0.06, 13.50, 21.83, 24.89, 31.15,
31.73, 32.17, 40.70, 42.93, 140.53, 140.89, 211.96.
1H NMR (400 MHz, CDCl3): = 0.00 (s, 9 H), 0.88 (t, J = 7.1 Hz,
3 H), 1.26–1.31 (m, 4 H), 2.15–2.21 (m, 2 H), ABX, A = 3.25,
B = 3.48, X = 4.30 (JAX = 6.9 Hz, JBX = 7.8 Hz, JAB = 16.2 Hz, 3
H), 6.04 (t, J = 7.6 Hz, 1 H), 7.15–7.25 (m, 5 H), 7.40–7.44 (m, 2
H), 7.50–7.54 (m, 1 H), 7.85–7.88 (m, 2 H).
13C NMR (100 MHz, CDCl3): = 0.57, 14.17, 22.56, 31.93, 32.38,
45.20, 45.93, 126.20, 128.08, 128.25, 128.45, 128.56, 132.83,
137.70, 140.21, 142.19, 144.34, 199.30.
MS (EI): m/z (%) = 364 (M+, 6), 73 (100).
MS (EI): m/z (%) = 253 (M+ + 1, 3), 73 (100).
Anal. Calcd for C24H32OSi: C, 79.06; H, 8.85. Found: C, 79.11; H,
8.89.
Anal. Calcd for C15H28OSi: C, 71.36; H, 11.18. Found: C, 71.35; H,
11.19.
(Z)-1-(4 -Methoxyphenyl)-3-phenyl-4-trimethylsilyl-4-nonen-1-
one (3g)
(Z)-1,3-Diphenyl-4-trimethylsilyl-4-decen-1-one (3k)
Yield: 83%; colorless oil.
Yield: 72%; colorless oil.
IR (neat): 2956, 1679, 1601, 1510, 1249, 1169, 1031, 837, 701 cm–1.
IR (neat): 2955, 2928, 1687, 1449, 1247, 838, 752 cm–1.
1H NMR (400 MHz, CDCl3): = 0.00 (s, 9 H), 0.88 (t, J = 7.1 Hz,
3 H), 1.30–1.32 (m, 4 H), 2.15–2.19 (m, 2 H), 3,85 (s, 3 H), ABX,
A = 3.19, B = 3.42, X = 4.29 (JAX = 7.1 Hz, JBX = 7.6 Hz,
1H NMR (400 MHz, CDCl3): = 0.00 (s, 9 H), 0.87 (t, J = 7.0 Hz,
3 H), 1.26–1.35 (m, 6 H), 2.15–2.20 (m, 2 H), ABX, A = 3.25,
B = 3.49, X = 4.31 (JAX = 6.9 Hz, JBX = 7.9 Hz, JAB = 16.2 Hz, 3
H), 6.05 (t, J = 7.3 Hz, 1 H), 7.15–7.54 (m, 8 H), 7.86–7.88 (m, 2
H).
JAB = 15.9 Hz, 3 H), 6.03 (t, J = 6.7 Hz, 1 H), 6.88 (d, J = 8.9 Hz,
2 H), 7.12–7.23 (m, 5 H), 7.85 (d, J = 8.9 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 0.59, 14.19, 22.56, 31.93, 32.41,
44.77, 46.05, 55.52, 113.68, 126.14, 128.47, 139.36,130.79,140.34,
142.08, 144.48, 163.30, 197.78.
13C NMR (100 MHz, CDCl3): = 0.49, 14.05, 22.64, 29.80, 31.62,
32.08, 45.12, 45.83, 126.12, 128.00, 128.17, 128.37, 128.48,
132.75, 137.61, 140.12, 142.15, 144.26, 199.21.
MS (EI): m/z (%) = 394 (M+, 4), 73 (100).
MS (EI): m/z (%) = 378 (M+, 4), 73 (100).
Anal. Cald for C25H34O2Si: C, 76.09; H, 8.68. Found: C, 76.11; H,
8.73.
Anal. Calcd for C25H34OSi: C, 79.31; H, 9.05. Found: C, 79.20; H,
9.36.
(Z)-1-(3 -Nitrophenyl)-3-phenyl-4-trimethylsilyl-4-nonen-1-one
(Z)-1-(4 -Methoxyphenyl)-3-phenyl-4-trimethylsilyl-4-decen-1-
(3h)
one (3l)
Yield: 56%; pale yellow oil.
Yield: 80%; colorless oil.
IR (neat): 2958, 1697, 1543, 1352, 1249, 909, 734 cm–1.
IR (neat): 2955, 1678, 1601, 1492, 1249, 1169, 837, 701 cm–1.
1H NMR (400 MHz, CDCl3): = 0.01 (s, 9 H), 0.89 (t, J = 7.3 Hz,
3 H), 1.31–1.33 (m, 4 H), 2.19–2.21 (m, 2 H), ABX, A = 3.32,
B = 3.48, X = 4.28 (JAX = 7.1 Hz, JBX = 7.7 Hz, JAB = 16.2 Hz, 3
H), 6.04 (t, J = 7.2 Hz, 1 H), 7.14–7.24 (m, 5 H), 7.61 (t, J = 8.0 Hz,
1 H), 8.16 (d, J = 7.8 Hz, 1 H), 8.37 (d, J = 8.1 Hz, 1 H), 8.62 (s, 1
H).
13C NMR (100 MHz, CDCl3): = 0.54, 14.16, 22.59, 31.94, 32.41,
45.37, 46.09, 123.01, 126.53, 127.16, 128.43, 129.82, 133.60,
138.87, 140.14, 142.08, 143.65, 197.35.
1H NMR (400 MHz, CDCl3): = 0.05 (s, 9 H), 0.91 (t, J = 7.0 Hz,
3 H), 1.26–1.41 (m, 6 H), 2.19–2.24 (m, 2 H), 3.88 (s, 3 H), ABX,
A = 3.23, B = 3.46, X = 4.34 (JAX = 7.0 Hz, JBX = 7.7 Hz,
JAB = 16.1 Hz, 3 H), 6.08 (t, J = 7.4 Hz, 1 H), 6.93 (d, J = 11.7 Hz,
2 H), 7.17–7.29 (m, 5 H), 7.90 (d, J = 11.7 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 0.58, 14.13, 22.71, 29.88, 31.68,
32.15, 44.74, 46.00, 55.48, 113.65, 126.12, 128.19, 128.45, 130.33,
130.75, 140.31, 142.09, 144.49, 163.29, 197.73.
MS (EI): m/z (%) = 408 (M+, 5), 73 (100).
MS (EI): m/z (%) = 409 (M+, 3), 73 (100).
Anal. Calcd for C26H36O2Si: C, 76.42; H, 8.88. Found: C, 76.44; H,
8.92.
Anal. Calcd for C24H31NO3Si: C, 70.38; H, 7.63. Found: C, 70.39;
H, 7.65.
(Z)-(3 -Nitrophenyl)-3-phenyl-4-trimethylsilyl-4-decen-1-one
(Z)-4-(4 -Nitrophenyl)-5-trimethylsilyl-5-decen-2-one (3i)
(3m)
Yield: 66%; pale yellow oil.
Yield: 54%; pale yellow oil.
IR (neat): 2957, 1719, 1605, 1520, 1347, 1249, 840 cm–1.
IR (neat): 2955, 1696, 1533, 1491, 1451, 1350, 1248, 838, 702 cm–1.
1H NMR (400 MHz, CDCl3): = 0.02 (s, 9 H), 0.93 (t, J = 7.2 Hz,
3 H), 1.36–1.41 (m, 2 H), 1.59–1.67 (m, 2 H), 2.07 (s, 3 H), 2.19–
2.22 (m, 2 H), ABX, A = 2.78, B = 2.94, X = 4.21 (JAX = 7.6 Hz,
JBX = 7.2 Hz, JAB = 16.8 Hz, 3 H), 6.06 (t, J = 7.6 Hz, 1 H), 7.34 (d,
J = 8.8 Hz, 2 H), 8.13 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 0.48, 14.08, 22.54, 30.64, 31.93,
32.25, 45.06, 49.62, 123.51, 129.12, 139.71, 143.68, 146.50,
152.15, 206.36.
1H NMR (400 MHz, CDCl3): = 0.02 (s, 9 H), 0.88 (t, J = 6.8 Hz,
3 H), 1.27–1.38 (m, 6 H), 2.17–2.23 (m, 2 H), ABX, A = 3.33,
B = 3.49, X = 4.29 (JAX = 7.2 Hz, JBX = 7.6 Hz, JAB = 16.0 Hz, 3
H), 6.06 (t, J = 7.2 Hz, 1 H), 7.15–7.24 (m, 5 H), 7.62 (t, J = 8.0 Hz,
1 H), 8.16 (d, J = 8.0 Hz, 1 H), 8.37 (dd, J = 8.0, 1.2 Hz, 1 H), 8.63
(t, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): = 0.53, 14.11, 22.69, 29.90, 31.72,
32.17, 45.38, 46.07, 123.00, 126.52, 127.13, 128.42, 129.80,
133.58, 138.89, 140.17, 142.15, 143.66, 197.31.
MS (EI): m/z (%) = 347 (M+, 1), 73 (100).
Synthesis 2002, No. 17, 2497–2502 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
(Z)-γ-Silyl-γ,δ-Unsaturated Ketones and their Application in the Synthesis of 1,4-Diketones
2501
MS (EI): m/z (%) = 423 (M+, 2), 73 (100).
MS (EI): m/z (%) = 359 (M+ + 1, 4), 135 (100).
Anal. Calcd for C25H33NO3Si: C, 70.88; H, 7.85. Found: C, 70.87;
H, 7.88.
Anal. Calcd for C24H22O3: C, 80.42; H, 6.19. Found: C, 80.43; H,
6.21.
(Z)-4-(4 -Nitrophenyl)-5-trimethylsilyl-5-undecen-2-one (3n)
1-(Cyclohexanon-3-yl)-2-phenyl-1-acetone (5c)20
Yield: 59%; pale yellow oil.
Yield: 69%; colorless oil.
IR (neat): 2956, 1719, 1520, 1346, 839 cm–1.
IR (neat): 3029, 2927, 1718, 1681, 1599, 1249, 1165, 788 cm–1.
1H NMR (400 MHz, CDCl3): = 0.02 (s, 9 H), 0.91 (t, J = 7.1 Hz,
3 H), 1.29–1.42 (m, 6 H), 2.08 (s, 3 H), 2.17–2.23 (m, 2 H), ABX,
A = 2.77, B = 2.95, X = 4.21 (JAX = 7.9 Hz, JBX = 6.8 Hz,
JAB = 16.6 Hz, 3 H), 6.06 (t, J = 7.4 Hz, 1 H), 7.34 (d, J = 8.8 Hz,
2 H), 8.12 (d, J = 8.8 Hz, 2 H).
1H NMR (400 MHz, CDCl3): = 1.55–1.71 (m, 2 H), 1.84–2.01 (m,
2 H), 2.10–2.29 (m, 3 H), 2.36–2.51 (m, 1 H), 2.85–2.91 (m, 1 H),
3.63 (s, 2 H), 7.10–7.35 (m, 5 H).
MS (EI): m/z (%) = 216 (M+, 4), 105 (100).
13C NMR (100 MHz, CDCl3): = 0.55, 14.15, 22.69, 29.82, 30.72,
31.75, 32.24, 45.10, 49.68, 123.57, 129.20, 139.76, 143.79, 146.55,
152.22, 206.42.
1,3-Diphenylnonane-1,4-dione (5d)21
Yield: 80%; colorless oil.
IR (neat): 3054, 2931, 1715, 1685, 754, 701 cm–1.
1H NMR (400 MHz, CDCl3): = 0.82 (t, J = 6.9 Hz, 3 H), 1.14–
1.22 (m, 2 H), 1.23–1.40 (m, 2 H), 1.51–1.63 (m, 2 H), 2.46–2.50
(m, 1 H), 2.56–2.60 (m, 1 H), ABX, A = 3.12, B = 4.03, X = 4.20
(JAX = 3.7 Hz, JBX = 10.1 Hz, JAB = 18.0 Hz, 3 H), 7.27–7.53 (m, 8
H), 7.93–7.96 (m, 2 H).
MS (EI): m/z (%) = 361 (M+, 1), 73 (100).
Anal. Calcd for C20H31NO3Si: C, 66.44; H, 8.64. Found: C, 66.45;
H, 8.67.
(Z)-1-(Cyclohexanone-3-yl)-1-trimethylsilyl-1-heptene (3o)
Yield: 60%; colorless oil.
IR (neat): 2956, 2859, 1715, 1611, 1448, 1249, 837 cm–1.
1H NMR (400 MHz, CDCl3): = 0.14 (s, 9 H), 0.89 (t, J = 7.0 Hz,
3 H), 1.26–1.35 (m, 5 H), 1.36–1.56 (m, 1 H), 1.56–1.92 (m, 3 H),
2.00–2.20 (m, 3 H), 2.24–2.48 (m, 5 H), 5.97 (t, J = 7.2 Hz, 1 H).
MS (EI): m/z (%) = 309 (M+ + 1, 8), 105 (100).
1-(Cyclohexanon-3-yl)-1-hexanone (5e)21
Yield: 85%; colorless oil.
IR (neat): 2934, 2871, 1713, 1129, 733 cm–1.
13C NMR (400 MHz, CDCl3): = 0.52, 14.06, 22.64, 25.48, 29.81,
31.58, 31.99, 32.75, 41.28, 43.50, 48.56, 141.13, 141.43, 212.61.
MS (EI): m/z (%) = 266 (M+, 1), 73 (100).
1H NMR (400 MHz, CDCl3): = 0.89 (t, J = 7.2 Hz, 3 H), 1.20–
1.35 (m, 4 H), 1.56–1.63 (m, 2 H), 1.64–1.80 (m, 2 H), 2.05–2.15
(m, 2 H), 2.33–2.67 (m, 6 H), 2.88–2.92 (m, 1 H).
MS (EI): m/z (%) = 197 (M+ + 1, 15), 43 (100).
Anal. Calcd for C16H30OSi: C, 72.11; H, 11.35. Found: C, 72.09; H,
11.36.
1,3-Diphenyldecane-1,4-dione (5f)
Colorless oil; yield: 88%.
IR (neat): 2929, 2857, 1715, 1685, 1494, 754, 701 cm–1.
1,4-Diketones 5a–g; General Procedure
To the solution of MCPBA (0.3mmol) in CH2Cl2 (10mL) was added
(Z)- -silyl , -unsaturated ketone 3 (0.3mmol). The mixture was
stirred at r.t. until the vinylsilane disappeared. The mixture was
washed in turn with sat. aq NaHCO3, sat. brine and H2O. CH2Cl2
was rotary evaporated and a solution of TFA (0.33 mmol) in MeOH
(10mL) was added. After refluxing for 2 h, the reaction was worked
up and a pure product was obtained by column chromatography (sil-
ica gel; light petroleum–EtOAc, 15:1).
1H NMR (400 MHz, CDCl3): = 0.83 (t, J = 7.1 Hz, 3 H), 1.18–
1.25 (m, 6 H), 1.49–1.56 (m, 2 H), 2.47–2.51 (m, 1 H), 2.57–2.61
(m, 1 H), ABX, A = 3.12, B = 4.04, X = 4.42 (JAX = 3.6 Hz,
JBX = 10.2 Hz, JAB = 18.0 Hz, 3 H), 7.27–7.57 (m, 8 H), 7.95–7.97
(m, 2 H).
13C NMR (100 MHz, CDCl3): = 14.02, 22.48, 23.60, 28.69, 31.53,
41.86, 42.37, 53.32, 127.52, 128.10, 128.38, 128.56, 129.10,
133.20, 136.56, 138.25, 198.27, 209.49.
1,3,5-triphenylpentane-1,4-dione (5a)
Yield: 81%; white solid; mp 78–80°C (hexane) (Lit.19 79–80 °C).
MS (EI): m/z (%) = 323 (M+ + 1, 23), 105 (100).
IR (KBr): 3062, 2925, 1719, 1685, 1598, 1449, 788, 757, 700 cm–1.
Anal. Calcd for C22H26O2: C, 81.95; H, 8.13. Found: C, 81.90; H,
8.15.
1H NMR (400 MHz, CDCl3): = ABX, A = 3.15, B = 4.01,
X = 4.53 (JAX = 3.84 Hz, JBX = 10.0 Hz, JAB = 18.1 Hz, 3 H), 3.85
(A B , J = 10.8 Hz, 2 H), 7.05–7.52 (m, 13 H), 7.92–7.95 (m, 2 H).
1-(4 -Methoxylphenyl)-3-phenyldecane-1,4-dione (5g)
Yield: 75%; colorless oil.
MS (EI): m/z (%) = 328 (M+, 1), 105 (100).
IR (neat): 2930, 1756, 1715, 1675, 1601, 1506, 1249, 1195, 701
cm–1.
1-(4 -methoxylpenyl)-3,5-diphenylpentane-1,4-dione (5b)
1H NMR (400 MHz, CDCl3): = 0.81 (t, J = 7.1 Hz, 3 H), 1.14–
1.21 (m, 6 H), 1.40–1.63 (m, 2 H), 2.39–2.47 (m, 2 H), ABX,
A = 2.78, B = 3.42, X = 4.25 (JAX = 5.2 Hz, JBX = 9.8 Hz,
Yield: 84%; pale yellow oil.
IR (neat): 3028, 2926, 1719, 1674, 1601, 1510, 1249, 1169, 1031,
700 cm–1.
1H NMR (400 MHz, CDCl3): = ABX, A = 3.12, B = 3.96,
X = 4.51 (JAX = 3.8 Hz, JBX = 10.0 Hz, JAB = 17.9 Hz, 3 H), 3.85 (s,
3 H), 3.85 (A B , J = 6.8 Hz, 2 H), 6.89 (d, J = 8.9 Hz, 2 H), 7.22–
7.33 (m, 5 H), 7.92 (d, J = 8.9 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 39.5, 43.7, 46.9, 56.0, 114.0,
126.9, 127.1, 128.4, 128.6, 129.3, 129.4, 129.6, 129.7, 134.3, 134.5,
166.4, 197.6, 207.1.
JAB = 17.0 Hz, 3 H), 3.77 (s, 3 H), 6.85 (d, J = 8.8 Hz, 2 H), 7.24–
7.36 (m, 5 H), 7.93 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): = 14.0, 23.1, 32.2, 24.2, 29.5, 38.2,
39.5, 47.3, 56.0, 113.5, 126.9, 128.6, 129.3, 129.6, 129.7, 134.3,
166.4, 197.6, 208.2.
MS (EI): m/z (%) = 353 (M+ + 1, 4), 124 (100).
Anal. Calcd for C23H28O3: C, 78.38; H, 8.01. Found: C, 78.32; H,
8.05.
Synthesis 2002, No. 17, 2497–2502 ISSN 0039-7881 © Thieme Stuttgart · New York

2502
W. Zheng, X. Huang
PAPER
X-Ray Crystal Data of 3d
References
The X-ray structural analysis of 3d (single crystal, Figure 1) crys-
tallized from a hexane, colorless crystal, C21H25NO3Si (367.51); tri-
clinic P – 1 with a = 7.6678(16), b = 11.185(2), c = 13.075(3) Å,
= 73.239(4)°, = 84.132(4)°, = 80.324(4)°, V = 1056.7(4) Å 3,
Z = 2, D = 1.155 Mg/m3, absorption coefficient 0.129 mm–1 was
performed at 293(2) K using graphite monochromated MoK radi-
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ation ( = 0.71073 Å, limiting indices –10
h 7, –14 k 14, –16
l 17, -range for data collection 1.63 to 28.29, reflections mea-
sured 6435, unique reflections 4657 (Rint = 0.0614). Completeness
to = 28.29° 88.6%, data/restraints/parameters = 4657/10/313. The
structure was solved by direct methods and refined by full-matrix
least-squares on F2 using SHELXL-97 (Sheldrick, 1997) program
system. All non-hydrogen atoms were refined anisotropically and
the position of the hydrogen atoms was calculated as a riding model.
The weighting scheme was w–1 = s2(Fo)2 + (0.0785P)2 + 0.0000P
(5) (a) Huang, X.; Xu, X.; Zheng, W. Synth. Commun. 1999, 29,
2399. (b) Sun, A.; Huang, X. J. Synthesis 2000, 775.
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(11) CCDC-189354 contains the supplementary crystallographic
data for this paper.
(12) Yamaguchi, R.; Kawsaki, H.; Kawanisi, M. Synth. Commun.
1982, 12, 1027.
(13) Seebach, D. Angew. Chem., Int. Ed. Engl. 1979, 18, 239.
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Wiley: London, 1951, 78.
with P = 1/3(Fo +2Fc2). Goodness-of-fit on F2 0.786; final R indices
2
[I > 2 (I)], R1 = 0.0550, wR2 = 0.1195; R indices (all data)
R1 = 0.1520, wR2 = 0.1812.
Selected bond distances [pm] and bond angles [°]: Si–C(8)
1.896(3), C(6)–C(7) 1.482(4), C(7)–C(8) 1.335(4), C(7)–H(6)
0.92(3), C(8)–C(9) 1.538(4), C(9)–C(10) 1.515(4), C(9)–C(16)
1.531(5), C(9)–H(7) 0.99(3), C(16)–C(17) 1.499(5), C(16)–H(12)
0.997(17), C(16)–H(13) 0.981(18), C(17)–C(18) 1.486(5), C(8)–
C(7)–C(6) 127.0(4), C(8)–C(7)–H(6) 121.2(19), C(6)–C(7)–H(6)
111.4(19), C(7)–C(8)–C(9) 119.8(3), C(7)–C(8)–Si 124.0(3), C(9)–
C(8)–Si 116.2(2), C(8)–C(9)–H(7) 105.5(15), C(17)–C(16)–C(9)
114.6(3), C(17)–C(16)–H(12) 104.2(17), C(9)–C(16)–H(12)
108.7(18), C(17)–C(16)–H(13) 109.4(19), C(9)–C(16)–H(13)
109.3(19), H(12)–C(16)–H(13) 110(3), O(1)–C(17)–C(18)
121.0(4), O(1)–C(17)–C(16) 122.1(4).
(16) Corbett, R. E.; Davey, C. L. J. Chem. Soc. 1955, 291.
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(20) Katritrky, A. R.; Yang, Z. J.; Lam, J. N. J. Org. Chem. 1991,
56, 6917.
Acknowledgment
This work was supported by the Natural Science Foundation of Chi-
na (Project No. 20272052), the Doctoral Program Foundation of
National Education Ministry of China, and the State Key Laborato-
ry of Organometallic Chemistry, Shanghai Institute of Organic Che-
mistry, Chinese Academy of Sciences.
(21) Katritzky, A. R.; Lang, H.; Wang, Z.; Lie, Z. J. Org. Chem.
1996, 61, 7551.
Synthesis 2002, No. 17, 2497–2502 ISSN 0039-7881 © Thieme Stuttgart · New York