Novel stereoselective synthesis of 1,3-dien-2-yl esters by a palladiumcatalysed cross-coupling reaction of (E)-α-iodo-α,β- unsaturated esters

Article abstract of DOI:10.3184/030823410X12733373355395

(E)-α-Stannyl-α,β-unsaturated esters underwent an iododestannylation reaction to afford (E)-α-iodo-α,β- unsaturated esters, which reacted with (E)-alkenylzirconium(IV) complexes produced in situ by hydrozirconation of terminal alkynes in the presence of P

Full text of DOI:10.3184/030823410X12733373355395

266 RESEARCH PAPER
MAY, 266–268
JOURNAL OF CHEMICAL RESEARCH 2010
Novel stereoselective synthesis of 1,3-dien-2-yl esters by a palladium-
catalysed cross-coupling reaction of (E)-α-iodo-α,β-unsaturated esters
Weisen Yang, Junmin Chen, Wenyan Hao and Mingzhong Cai*
Department of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
(E)-α-Stannyl-α,β-unsaturated esters underwent an iododestannylation reaction to afford (E)-α-iodo-α,β-unsaturated
esters, which reacted with (E)-alkenylzirconium(IV) complexes produced in situ by hydrozirconation of terminal
alkynes in the presence of Pd(PPh3)4 to afford stereoselectively a variety of 1,3-dien-2-yl esters in good yields.
Keywords: hydrozirconation, functionalised 1,3-diene, palladium, cross-coupling, iododestannylation, 1,3-dien-2-yl esters
The stereoselective synthesis of conjugated dienes has attracted
considerable interest in organic chemistry because of their
appearance in a wide variety of biologically active molecules
and because they are key synthetic intermediates.1,2 The syn-
thesis of 1,3-dienes for use in the Diels–Alder reaction is still
an important challenge in organic synthesis3 although other
elegant uses of these compounds have been developed.4 The
transition metal-catalysed cross-coupling reactions of stereo-
defined vinyl halides with vinyl organometallic compounds
have provided a straightforward and convenient route for the
stereocontrolled synthesis of conjugated dienes.5,6 Kasatkin
and Whitby reported the insertion of 1-lithio-1-halobutadiene
into organozirconocenes providing a stereocontrolled synthe-
sis of (E,Z)-1,3-dienes.7 Recently, Molander and Yokoyama
reported one-pot stereoselective synthesis of trisubstituted
1,3-dienes via sequential Suzuki–Miyaura cross-coupling with
alkenyl- and alkyl-trifluoroborates.8
The stereocontrolled synthesis of functionalised 1,3-dienes
is also of high interest in organic synthesis.9 Heteroatom-sub-
stituted 1,3-dienes are useful precursors to construct highly
functionalised ring systems in Diels–Alder reactions.10,11 The
stereoselective synthesis of 1,3-dienylsilanes,12–14 1,3-dienyl
sulfides,15–17 1,3-dienyl selenides,18–20 1,3-dienyl sulfones,21,22
and 1,3-dienylstannanes23–25 has already been described in the
literature. 2-Alkoxycarbonyl-substituted 1,3-dienes have been
extensively studied in recent years as potential starting materi-
als for organic synthesis, in particular for various [4 + 2] cyclo-
additions. A number of these compounds have proved to be
valuable precursors for functionalised alkyl 1-cyclohexene-1-
carboxylates,26 naturally occurring cyclopentanoid terpenic
acids,27 and biologically important litsenolides.28 Many meth-
ods for the synthesis of 2-alkoxycarbonyl-substituted 1,3-
dienes have been developed including aldol-type condensation
of metallated alkene carboxylates,27,28 Wittig olefination
of aldehydes,29 titanium(IV) chloride catalysed reaction of
1-ethoxy-3-trimethylsilylprop-1-yne with 1-haloketones,30
Pd(0)-catalysed coupling of lithium (α-alkoxycarbonyl)alkenyl
cuprates with vinyl halides,31 and the Horner-Emmons reaction
of the allylphosphonates with aldehydes.32 Recently, Aggarwal
et al. have reported the synthesis of 2-ethoxycarbonyl-
substituted 1,3-dienes from aldehydes and ethyl acrylate in
the presence of a phosphine and a Lewis acid through a
modification of the Morita reaction.33 Despite considerable
methodological differentiation, the reported procedures mostly
suffer from some drawbacks such as limited scope,27,28 scarce
availability of substrates,30–32 moderate yields,28,29 and low
stereoselectivity.33 We now report that 1,3-dien-2-yl esters can
be conveniently synthesised stereoselectively by the palla-
dium-catalysed cross-coupling reaction of (E)-α-iodo-α,β-
unsaturated esters with (E)-alkenylzirconium(IV) complexes
produced in situ by hydrozirconation of terminal alkynes.
Palladium-catalysed hydrostannylation of alkynyl esters can
proceed highly regio- and stereoselectively, affording (E)-α-
stannyl-α,β-unsaturated esters in high yields.34 (E)-α-Stannyl-
α,β-unsaturated esters were subjected to an iododestannylation
reaction under mild conditions to afford (E)-α-iodo-α,β-
unsaturated esters 1 in high yields (Scheme 1).
(E)-α-Iodo-α,β-unsaturated esters 1 are difunctional group
reagents in which two synthetically versatile groups are linked
to the same olefinic carbon atom and can be considered both
as vinyl iodides and α,β-unsaturated esters. It is well known
that vinyl iodides can undergo a palladium-catalysed cross-
coupling reaction with alkenylzirconium(IV) complexes to
give 1,3-dienes with retention of configuration.35 With a
convenient route to the (E)-α-iodo-α,β-unsaturated esters 1
we decided to investigate the feasibility of using 1 in
palladium-catalysed cross-coupling reaction with (E)-
alkenylzirconium(IV) complexes 2. We observed that, when
the cross-coupling reactions of 1 with a variety of (E)-
alkenylzirconium(IV) complexes 2 produced in situ by hydro-
zirconation of terminal alkynes were performed in THF at
room temperature using Pd(PPh3)4 as a catalyst (Scheme 2),
fairly rapid reactions occurred affording stereoselectively the
desired coupled products 3 in good yields. The experimental
results are summarised in Table 1.
The 3E-configuration of the compounds 3a–k was estab-
1
lished by their H NMR spectra which show a doublet at δ =
6.00–6.88 with a coupling constant of 15.6–16.4 Hz, indicat-
ing the retention of the E-configuration of the starting com-
pounds 2. In addition, the 1Z-configuration of the compound
3c was confirmed by the NOESY in the 1H NMR spectrum. An
enhancement of the allylic protons was observed as the vinylic
Scheme 1
* Correspondent. E-mail: caimzhong@163.com

JOURNAL OF CHEMICAL RESEARCH 2010 267
Scheme 2
Table 1 Synthesis of 1,3-dien-2-yl esters (3a–k)
MS (EI, 70 eV): m/z 282 (M+, 57), 203 (84), 91 (100). Anal. Calcd for
C9H15O2I: C, 38.30; H, 5.36. Found: C, 38.03; H, 5.17%.
Entry
R
R1
Product
Yielda/%
(E)-1-(Ethoxycarbonyl)-1-iodo-2-phenylethene (1b): Oil. IR (film):
ν (cm−1) 3059, 2981, 1721, 1604, 1575, 1494, 1446, 1369, 1211, 1024,
752, 693; 1H NMR (400 MHz, CDCl3): δ 7.50 (s, 1H), 7.35–7.23 (m,
5H), 4.22 (q, J = 7.2 Hz, 2H), 1.18 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 166.2, 146.2, 136.5, 128.9, 128.4, 127.9, 84.5, 62.4,
13.7; MS (EI, 70 eV): m/z 302 (M+, 17), 223 (100), 193 (77), 176 (71).
Anal. Calcd for C11H11O2I: C, 43.72; H, 3.67. Found: C, 43.89;
H, 3.53%.
1
2
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
n-C4H9
3a
3b
3c
3d
3e
3f
3g
3h
3i
78
83
72
80
84
73
79
82
78
81
76
Ph
3
CH3OCH2
n-C6H13
CH3OCH2CH2
CH3OCH2
Ph
n-C4H9
n-C6H13
CH3OCH2CH2
CH3OCH2CH2
4
5
6
7
Ph
8
Ph
(E)-1-(Ethoxycarbonyl)-1-iodooct-1-ene (1c): Oil. IR (film): ν
1
(cm−1) 2928, 2857, 1715, 1608, 1465, 1368, 1215; H NMR (400
9
Ph
10
11
Ph
3j
3k
MHz, CDCl3): δ 6.89 (t, J = 7.2 Hz, 1H), 4.25 (q, J = 7.2 Hz, 2H),
2.50–2.42 (m, 2H), 1.46–1.24 (m, 11H), 0.89 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 163.9, 156.2, 84.5, 62.2, 33.4, 31.5,
28.8, 28.7, 22.6, 14.1, 13.9; MS (EI, 70 eV): m/z 310 (M+, 91), 109
(100). Anal. Calcd for C11H19O2I: C, 42.58; H, 6.17. Found: C, 42.29;
H, 6.31%.
n-C6H13
a Isolated yield based on (E)-α-iodo-α,β-unsaturated ester 1
used.
proton (δ = 5.92) of 3c was irradiated. There was no correla-
tion between the allylic protons (δ = 2.26–2.32) and the vinylic
proton (δ = 6.24). The correlation between the vinylic proton
(δ = 5.92) and another vinylic proton (δ = 6.24) was observed.
The NOE results indicate that 3c has the expected 1Z-
configuration and the palladium-catalysed cross-coupling
reaction of (E)-α-iodo-α,β-unsaturated esters 1 with (E)-
alkenylzirconium(IV) complexes 2 occurs with the configura-
tion retention of both the starting compounds 1 and the
compounds 2.
In conclusion, a convenient synthetic method for 1,3-
dien-2-yl esters has been developed by the palladium-catalysed
cross-coupling reactions of (E)-α-iodo-α,β-unsaturated esters
with (E)-alkenylzirconium(IV) complexes. The present method
has the advantages of readily available starting materials,
straightforward and simple procedures, mild reaction condi-
tions, high stereoselectivity, and good yields.
Synthesis of 1,3-dien-2-yl esters 3a–k; general procedure
A dry 25 mL round-bottomed flask was charged with Cp2Zr(H)Cl
(1.1 mmol) under argon. THF (4 mL) was injected, followed by
addition of the terminal alkyne (1.1 mmol). The mixture was stirred
at room temperature for 40 min to yield a clear solution of (E)-
alkenylzirconium(IV) complex 2. (E)-α-iodo-α,β-unsaturated ester 1
(1 mmol) and Pd(PPh3)4 (0.05 mmol) were the added and the mixture
stirred at room temperature for 12 h. The mixture was diluted with
diethyl ether (25 mL) and the diluted mixture was filtered through
a short plug of silica gel and concentrated to give a residue, which
was purified by column chromatography on silica gel (eluent: light
petroleum ether/EtOAc, 19:1).
(5Z,7E)-6-(Ethoxycarbonyl)dodeca-5,7-diene (3a): Oil. IR (film):
ν (cm−1) 2959, 2931, 2873, 1717, 1650, 1465, 1226, 1120, 696; H
1
NMR (400 MHz, CDCl3): δ 6.00 (d, J = 15.6 Hz, 1H), 5.75 (t, J = 7.6
Hz, 1H), 5.68 (dt, J = 15.6, 7.2 Hz, 1H), 4.27 (q, J = 7.2 Hz, 2H),
2.25–2.20 (m, 2H), 2.10–2.06 (m, 2H), 1.43–1.25 (m, 11H), 0.92–0.85
(m, 6H); 13C NMR (100 MHz, CDCl3): δ 168.2, 136.2, 133.4, 131.8,
127.8, 60.5, 32.6, 31.4, 31.3, 29.3, 22.3, 22.2, 14.3, 13.9; MS (EI,
70 eV): m/z 238 (M+, 6.4), 209 (22), 149 (100), 85 (61), 57 (82). Anal.
Calcd for C15H26O2: C, 75.58; H, 10.99. Found: C, 75.31; H, 10.76%.
(1E,3Z)-1-Phenyl-3-(ethoxycarbonyl)octa-1,3-diene (3b): Oil. IR
(film): ν (cm−1) 3131, 2958, 2929, 2871, 1718, 1619, 1452, 1227,
1096, 698; 1H NMR (400 MHz, CDCl3): δ 7.40–7.20 (m, 5H), 6.74 (d,
J = 16.4 Hz, 1H), 6.58 (d, J = 16.4 Hz, 1H), 6.02 (t, J = 7.6 Hz, 1H),
4.34 (q, J = 7.2 Hz, 2H), 2.35–2.29 (m, 2H), 1.49–1.22 (m, 7H), 0.92
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 167.9, 139.3,
137.2, 133.5, 129.3, 128.6, 127.5, 126.9, 126.4, 60.7, 31.4, 29.7, 22.4,
14.4, 13.9; MS (EI, 70 eV): m/z 258 (M+, 33), 229 (15), 201 (28),
105 (100), 77 (61). Anal. Calcd for C17H22O2: C, 79.03; H, 8.58.
Found: C, 78.85; H, 8.31%.
(2E,4Z)-1-Methoxy-4-(ethoxycarbonyl)nona-2,4-diene (3c): Oil.
IR (film): ν (cm−1) 3064, 2929, 1713, 1450, 1402, 1198, 1095, 698;
1H NMR (400 MHz, CDCl3): δ 6.24 (d, J = 16.0 Hz, 1H), 5.92 (t, J =
7.6 Hz, 1H), 5.80 (dt, J = 16.0, 5.2 Hz, 1H), 4.27 (q, J = 7.2 Hz, 2H),
3.97 (d, J = 5.2 Hz, 2H), 3.34 (s, 3H), 2.32–2.26 (m, 2H), 1.43–1.25
(m, 7H), 0.92 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ 167.6, 139.7, 132.4, 130.3, 126.6, 72.8, 60.6, 58.0, 31.3, 29.4, 22.3,
14.3, 13.8; MS (EI, 70 eV): m/z 226 (M+, 17), 197 (65), 73 (100),
57 (95). Anal. Calcd for C13H22O3: C, 68.99; H, 9.80. Found: C, 68.71;
H, 9.68%.
Experimental
1
IR spectra were obtained using a Perkin-Elmer 683 instrument. H
NMR spectra were recorded on a Bruker AC-P400 (400 MHz) spec-
trometer with TMS as an internal standard using CDCl3 as the solvent.
13C NMR spectra were recorded on a Bruker AC-P400 (100 MHz)
spectrometer using CDCl3 as the solvent. Mass spectra were obtained
on a Finnigan 8239 mass spectrometer. Microanalyses were obtained
using a Perkin-Elmer 240 elemental analyzer. All reactions were car-
ried out in pre-dried glassware (150 °C, 4 h) and cooled under a stream
of dry Ar. All solvents were dried, deoxygenated and freshly distilled
before use.
Synthesis of (E)-α-iodo-α,β-unsaturated esters 1a–c; general
procedure
A solution of iodine (1.7 mmol) in dry CH2Cl2 (10 mL) was
added dropwise to a solution of (E)-α-stannyl-α,β-unsaturated ester
(1.5 mmol) in dry CH2Cl2 (10 mL) over 30 min at 0 °C under argon.
After being stirred for 30 min at 0 °C, the mixture was stirred for 1 h
at room temperature and quenched with sat. aq. Na2S2O3 (5 mL).
The organic layer was washed with sat. aq. Na2S2O3 (5 mL) and water
(3 × 5 mL) and dried (MgSO4). Removal of the solvent under a reduced
pressure gave an oil, which was purified by column chromatography
on silica gel (eluent: light petroleum ether/EtOAc, 19:1).
(5Z,7E)-6-(Ethoxycarbonyl)tetradeca-5,7-diene (3d): Oil. IR
(film): ν (cm−1) 2928, 1727, 1606, 1464, 1378, 1156, 962, 862; H
1
(E)-1-(Ethoxycarbonyl)-1-iodohex-1-ene (1a): Oil. IR (film):
1
ν (cm−1) 2959, 1714, 1607, 1465, 1367, 1216; H NMR (400 MHz,
NMR (400 MHz, CDCl3): δ 6.02 (d, J = 16.0 Hz, 1H), 5.77 (t, J = 7.6
Hz, 1H), 5.69 (dt, J = 16.0, 7.6 Hz, 1H), 4.30 (q, J = 7.2 Hz, 2H),
2.27–2.20 (m, 2H), 2.13–2.06 (m, 2H), 1.45–1.21 (m, 15H), 0.91–0.85
(m, 6H); 13C NMR (100 MHz, CDCl3): δ 168.3, 136.1, 133.6, 131.9,
CDCl3): δ 6.90 (t, J = 7.6 Hz, 1H), 4.25 (q, J = 7.2 Hz, 2H), 2.49–2.43
(m, 2H), 1.45–1.25 (m, 7H), 0.90 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 163.9, 156.5, 84.5, 62.2, 33.1, 30.8, 22.2, 14.1, 13.8;

268 JOURNAL OF CHEMICAL RESEARCH 2010
1
127.7, 60.5, 32.9, 31.7, 31.4, 29.3, 29.1, 28.9, 22.6, 22.3, 14.3, 14.1,
13.9; MS (EI, 70 eV): m/z 266 (M+, 100), 221 (45), 177 (20). Anal.
Calcd for C17H30O2: C, 76.64; H, 11.35. Found: C, 76.37; H, 11.09%.
(3E,5Z)-1-Methoxy-5-(ethoxycarbonyl)deca-3,5-diene (3e): Oil. IR
963; H NMR (400 MHz, CDCl3): δ 6.08 (d, J = 15.6 Hz, 1H), 5.81
(t, J = 7.6 Hz, 1H), 5.69 (dt, J = 15.6, 7.6 Hz, 1H), 4.27 (q, J = 7.2 Hz,
2H), 3.43 (t, J = 6.8 Hz, 2H), 3.34 (s, 3H), 2.40–2.33 (m, 2H), 2.26–
2.21 (m, 2H), 1.44–1.26 (m, 11H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ 168.0, 137.6, 133.1, 129.7, 127.5, 72.1, 60.6,
58.6, 33.3, 31.7, 29.7, 29.2, 29.0, 22.6, 14.3, 13.9; MS (EI, 70 eV):
m/z 268 (M+, 51), 237 (35), 222 (100). Anal. Calcd for C16H28O3:
C, 71.60; H, 10.52. Found: C, 71.37; H, 10.29%.
1
(film): ν (cm−1) 2929, 1725, 1464, 1380, 1155, 1121, 964; H NMR
(400 MHz, CDCl3): δ 6.08 (d, J = 15.6 Hz, 1H), 5.81 (t, J = 7.6 Hz,
1H), 5.69 (dt, J = 15.6, 7.6 Hz, 1H), 4.27 (q, J = 7.2 Hz, 2H), 3.43
(t, J = 6.8 Hz, 2H), 3.34 (s, 3H), 2.40–2.34 (m, 2H), 2.27–2.22
(m, 2H), 1.43–1.27 (m, 7H), 0.89 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 168.0, 137.5, 133.1, 129.7, 127.5, 72.1, 60.5, 58.6,
33.3, 31.4, 29.3, 22.3, 14.3, 13.9; MS (EI, 70 eV): m/z 240 (M+, 55),
221 (45), 209 (26), 194 (100). Anal. Calcd for C14H24O3: C, 69.96;
H, 10.07. Found: C, 69.72; H, 10.19%.
(1Z,3E)-1-Phenyl-2-(ethoxycarbonyl)-5-methoxypenta-1,3-diene
(3f): Oil. IR (film): ν (cm−1) 3065, 2959, 2873, 1717, 1619, 1466,
1380, 1153, 1096, 965, 893, 792; 1H NMR (400 MHz, CDCl3):
δ 7.35–7.26 (m, 5H), 6.63 (s, 1H), 6.38 (d, J = 16.0 Hz, 1H), 5.86 (dt,
J = 16.0, 5.6 Hz, 1H), 4.25 (q, J = 7.2 Hz, 2H), 4.04 (d, J = 5.6 Hz,
2H), 3.37 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 168.8, 135.3, 133.4, 132.7, 130.5, 128.7, 128.5, 128.3,
128.2, 72.6, 61.3, 58.2, 13.9; MS (EI, 70 eV): m/z 246 (M+, 12), 202
(48), 115 (64), 105 (100), 77 (63). Anal. Calcd for C15H18O3: C, 73.15;
H, 7.37. Found: C, 72.87; H, 7.22%.
We thank the National Natural Science Foundation of China
(Project No. 20862008) and the Natural Science Foundation
of Jiangxi Province in China (2008GQH0034) for financial
support.
Received 26 March 2010; accepted 9 April 2010
Paper 1000030 doi: 10.3184/030823410X12733373355395
Published online: 8 June 2010
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1
804; H NMR (400 MHz, CDCl3): δ 7.45–7.24 (m, 10H), 6.88 (d,
4
5
J = 16.4 Hz, 1H), 6.75 (s, 1H), 6.64 (d, J = 16.4 Hz, 1H), 4.34 (q,
J = 7.2 Hz, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
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128.3, 128.0, 126.7, 61.5, 14.4; MS (EI, 70 eV): m/z 278 (M+, 24), 205
(100), 202 (37), 105 (82), 77 (25). Anal. Calcd for C19H18O2: C, 81.99;
H, 6.52. Found: C, 81.72; H, 6.38%.
(1Z,3E)-1-Phenyl-2-(ethoxycarbonyl)octa-1,3-diene (3h): Oil. IR
(filmt): ν (cm−1) 3067, 2927, 2854, 1716, 1494, 1451, 1094, 1027,
963, 756, 697; 1H NMR (400 MHz, CDCl3): δ 7.37–7.22 (m, 5H), 6.51
(s, 1H), 6.16 (d, J = 16.0 Hz, 1H), 5.80 (dt, J = 16.0, 7.2 Hz, 1H), 4.26
(q, J = 7.2 Hz, 2H), 2.20–2.13 (m, 2H), 1.45–1.25 (m, 4H), 1.23 (t,
J = 7.2 Hz, 3H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ 169.2, 135.7, 134.5, 134.2, 130.1, 128.7, 128.4, 128.1, 127.9, 61.2,
32.7, 31.2, 22.3, 14.0, 13.9; MS (EI, 70 eV): m/z 258 (M+, 2.4), 229
(15), 205 (35), 105 (100), 77 (44). Anal. Calcd for C17H22O2: C, 79.03;
H, 8.58. Found: C, 79.26; H, 8.35%.
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1
1022, 960, 696; H NMR (400 MHz, CDCl3): δ 7.30–7.23 (m, 5H),
6.51 (s, 1H), 6.16 (d, J = 15.6 Hz, 1H), 5.80 (dt, J = 15.6, 7.2 Hz, 1H),
4.26 (q, J = 7.2 Hz, 2H), 2.18–2.12 (m, 2H), 1.44–1.38 (m, 2H), 1.33–
1.25 (m, 6H), 1.21 (t, J = 7.2 Hz, 3H), 0.89 (t, J = 6.8 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 169.2, 135.7, 134.5, 134.3, 130.1, 128.7,
128.4, 128.1, 127.9, 61.1, 33.0, 31.7, 29.0, 28.9, 22.6, 14.1, 13.9; MS
(EI, 70 eV): m/z 286 (M+, 100), 241 (43), 159 (46), 143 (82), 129 (97).
Anal. Calcd for C19H26O2: C, 79.68; H, 9.15. Found: C, 79.40;
H, 9.29%.
(1Z,3E)-1-Phenyl-2-(ethoxycarbonyl)-6-methoxyhexa-1,3-diene
(3j): Oil. IR (film): ν (cm−1) 2928, 1725, 1448, 1381, 1225, 1147,
1118, 961, 753, 696; 1H NMR (400 MHz, CDCl3): 7.32–7.21 (m, 5H),
6.55 (s, 1H), 6.23 (d, J = 16.0 Hz, 1H), 5.80 (dt, J = 16.0, 7.2 Hz, 1H),
4.25 (q, J = 7.2 Hz, 2H), 3.46 (t, J = 6.8 Hz, 2H), 3.35 (s, 3H), 2.47–
2.41 (m, 2H), 1.20 (t, J = 7.2 Hz, 3H), 13C NMR (100 MHz, CDCl3):
δ 168.9, 135.6, 134.1, 131.1, 131.0, 130.5, 129.9, 128.4, 128.1, 71.8,
61.2, 58.7, 33.4, 13.9; MS (EI, 70 eV): m/z 260 (M+, 42), 215 (25),
201 (44), 169 (58), 155 (89), 159 (46), 141 (100), 128 (64). Anal.
Calcd for C16H20O3: C, 73.82; H, 7.74. Found: C, 73.56; H, 7.49%.
(3E,5Z)-1-Methoxy-5-(ethoxycarbonyl)dodeca-3,5-diene (3k): Oil.
IR (film): ν (cm−1) 2928, 2857, 1726, 1462, 1380, 1189, 1153, 1121,

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