Tandem Michael-Wittig-Horner reaction: Application to the synthesis of bisabolanes

Article abstract of DOI:10.1081/SCC-120015768

Bisabolane derivatives have been synthesized from para-substituted cinnamaldehydes according to a tandem Michael - Wittig - Horner reaction. This sequence was applied to a short access to (+/-)-ar-turmerone.

Full text of DOI:10.1081/SCC-120015768

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Tandem Michael–Wittig–Horner Reaction: Application to
the Synthesis of Bisabolanes
Olivier Chuzel a & Olivier Piva a
a Laboratoire de Chimie Organique , Photochimie et Synthèse , Université Claude Bernard
Lyon I , Villeurbanne Cedex, France
Published online: 17 Aug 2006.
To cite this article: Olivier Chuzel & Olivier Piva (2003) Tandem Michael–Wittig–Horner Reaction: Application to the Synthesis
of Bisabolanes, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
33:3, 393-402, DOI: 10.1081/SCC-120015768
To link to this article: http://dx.doi.org/10.1081/SCC-120015768
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 3, pp. 393–402, 2003
Tandem Michael–Wittig–Horner Reaction:
Application to the Synthesis of Bisabolanes
*
Olivier Chuzel and Olivier Piva
Laboratoire de Chimie Organique, Photochimie et Synthese,
Universite ClaudeBernard Lyon I,
Villeurbanne Cedex, France
ABSTRACT
Bisabolane derivatives have been synthesized from para-substituted
cinnamaldehydes according to a tandem Michael–Wittig–Horner
reaction. This sequence was applied to a short access to (þ/À)-
ar-turmerone.
Key Words: Michael addition; Wittig reaction; Bisabolanes;
Turmerone; Tandem reaction.
*Correspondence: Olivier Piva, Laboratoire de Chimie Organique, Photochimie
et Synthese, UMR 5622 CNRS, Universite ClaudeBernard Lyon I, Bat. Raulin,
43, Bd du 11 novembre 1918, 69622 Villeurbanne Cedex, France; Fax: 00-(0)4-72-
44-81-36; E-mail: piva@univ-lyon1.fr.
393
DOI: 10.1081/SCC-120015768
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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394
Chuzel and Piva
Recently, we reported a new tandem Michael–Wittig–Horner reac-
tion to prepare according to Sch. 1, ꢀ-substituted a-b-unsaturated esters
from alkenals or alkenones.[1] This sequence was based on the in situ
generation of an enolate which could further abstract the acidic hydrogen
atom of a phosphono derivative; therefore both components for the
Wittig–Horner reaction[2] could be formed and react.
This procedure was successfully applied to a two-step synthesis of E
and Z-ochtodenals, male sex pheromones of the boll weevil beetle. We
wish to present herein an access to other natural compounds like bisa-
bolanes in a similar way. Bisabolanes previously isolated from nature
exhibit numerous biological activities such as natural mosquitocide and
antibacterial properties.[3–9] Therefore, there is still an interest to develop
straightforward methods for the synthesis of these compounds.
Condensation of para-substituted benzaldehydes (1b, 1c, 1d) with
triethylphosphonoacetate (2) furnished a,b-unsaturated esters (3b, 3c,
3d) in good yields (Sch. 2). 1,2-Selective reduction[10] with Dibal-H
followed by oxidation using catalytic amounts of TEMPO according to
Einhorn’s conditions[11,12] lde to theformation of theunsaturatde
aldehydes (4b, 4c, 4d). Direct conversion of aldehyde (1d) into ester
(4d) in the presence of Ba(OH)2 according to a recent procedure[13] was
in our hands unsuccessful and deliver in place of the expected aldehyde,
compounds resulting from the well known Cannizzaro reaction.[14,15]
Treatment of aldehydes (4a, 4b, 4c, 4d) with Me2CuLi in diethyl ether
followed by (2) afforded in one single step ethyl (E )-5-aryl-hex-2-enoates
(5a, 5b, 5c, 5d) (Sch. 2). The E geometry of the new C¼C bond was easily
1
determined by H-NMR (typically JHa-Hb ¼ 15.1–15.6 Hz).
With aldehyde (4c), themajor adduct was thesecondary alcohol ( 6c)
resulting from a competitive 1,2-addition during the first step. This
reactivity could be attributed to the presence of the bromine atom
Scheme 1.

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Tandem Michael–Wittig–Horner Reaction
395
Scheme 2.
Scheme 3.
which could enhance the electrophilicity of the carbonyl group. Finally,
esters (5a, 5b, 5c, 5d) were submitted to the action of methyl Grignard
reagent to give tertiary alcohols (7a, 7b, 7c, 7d) in moderate to
good yields (Sch. 3). However, these tertiary allylic alcohols are prompt
to undergo an easy elimination of water during the acidic work-up.
In caseof ( 5d), for example, diene (8d) was isolated among numerous

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396
Chuzel and Piva
Scheme 4.
side-products, while with the other substrates, more complex reaction
products were formed probably according to Friedel–Crafts type
alkylations.[16–19]
Compound (7a) has also been converted in moderate yield by a
simple oxidative rearrangement using PCC[20–22] to (ꢀ)-ar-turmerone
(9) a natural product (Sch. 4), isolated as a major flavour component
of Zingiber and Curcuma species.[23–26]
In conclusion, we have been able to prepare in a two-step procedure
bisabolane derivatives from alkenals easily obtained from commercial
compounds. An access to (ꢀ)-ar-turmerone was also designed.
EXPERIMENTAL
The NMR spectra were recorded in CDCl3 or d6-benzene using a
Bruker AC 300 instrument. Fourier transform-IR spectra were carried
out in CHCl3 on a Perkin Elmer SpectroOne spectrometer. Mass spectra
were obtained on a Finigan-MAT 95 XL apparatus. Flash-chromato-
graphies were performed on silica gel 60 (40–63 mesh).
General Procedure for Preparation of Esters (3b–d)
To a suspension of sodium hydride (1.32 g, 33.0 mmol) in diethylether
(100 mL) was added dropwise ethyl 2-diethylphosphonopropionate
(7.40 g, 33.0 mmol) in the same solvent (20 mL). After 1 h at r.t. was
slowly added a solution of 4-substituted benzaldehyde (1) (3.60 g,
30.0 mmol) in the same solvent (10 mL). The reaction mixture was stirred
overnight at r.t. and carefully hydrolyzed with a saturated solution of
ammonium chloride (50 mL). After extraction with ether (3 ꢁ 50 mL),

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Tandem Michael–Wittig–Horner Reaction
397
the crude product was dried over MgSO4 and purified by flash-
chromatography (eluent: AcOEt/PE: 5/95) giving (3).
Ethyl 3-( p-methylphenyl)propenoate (3b, R5CH3)[27,28]: 5.36 g (94%).
1H-NMR (300 MHz, CDCl3): ꢀ 1.36 (3H, t, J ¼ 7.0 Hz), 2.40 (3H, s), 4.29
(2H, q, J ¼ 7.0 Hz), 6.41 (1H, d, J ¼ 16.0 Hz), 7.21 (2H, d, J ¼ 8.1 Hz), 7.44
(2H, d,J ¼ 8.1 Hz), 7.68(1H, d, J ¼ 16.0 Hz). IR:ꢁ ¼ 3017,2990,2944,1716,
1641, 1604, 1582, 1520, 1320, 1295, 1261, 1211, 1185, 1033, 834 cmÀ1
.
Ethyl 3-( p-bromophenyl)propenoate (3c, R5Br)[29]: 7.34 g (96%
1
yield). H-NMR (300 MHz, CDCl3): ꢀ 1.35 (3H, t, J ¼ 7.2 Hz), 4.28 (2H, q,
J ¼ 7.2 Hz), 6.44 (1H, d, J ¼ 16.0 Hz), 7.40 (2H, d, J ¼ 8.7 Hz), 7.53 (2H, d,
J ¼ 8.7 Hz), 7.63 (1H, d, J ¼ 16.0 Hz). IR: ꢁ ¼ 3015, 2985, 2941, 1712, 1639,
1606, 1582, 1515, 1368, 1288, 1259, 1183, 1035, 841 cmÀ1
.
Ethyl 3-(p-methoxyphenyl)propenoate (3d, R5OCH3)[30]: 5.44 g (88%
1
yield). H-NMR (300 MHz, CDCl3): ꢀ 1.35 (3H, t, J ¼ 7.2 Hz), 3.86 (3H,
s), 4.27 (2H, q, J ¼ 7.1 Hz), 6.33 (1H, d, J ¼ 15.8 Hz), 6.92 (2H, d,
J ¼ 9.0 Hz), 7.50 (2H, d, J ¼ 8.7 Hz), 7.66 (1H, d, J ¼ 15.8 Hz). IR:
ꢁ ¼ 3007, 2982, 2938, 2842, 1710, 1634, 1605, 1574, 1513, 1367, 1303,
1288, 1254, 1176, 1026, 832 cmÀ1
.
General Procedure for Preparation of Aldehydes (4b–d)
In a 500 mL two-necked flask was placed under nitrogen a solution of
ester (3) (27.9 mmol) in toluene (80 mL). After cooling to À78ꢂC, a 1.0 M
solution of Dibal (61.4 mL) in the same solvent was dropwise added. The
resulting mixture was stirred for 1 h, then carefully hydrolysed with aque-
ous solution of hydrochloric acid (40 mL). After addition of ether
(50 mL), the reaction was warmed to r.t. The organic layer was washed
with 1.0 N HCl solution (2 ꢁ 40 mL). The organic layers were dried over
MgSO4, filtered and concentrated under vacuo. To the crude mixture
diluted in CH2Cl2 (280 mL), were successively added TEMPO (0.44 g,
2.8 mmol), nBu4NCl (0.78 g, 2.8 mmol), a buffered solution of NaHCO3
(0.5 M) and K2CO3 (0.05 M) and finally NCS (7.45 g, 55.8 mmol). The
two phase solution was vigorously stirred overnight. After extraction of
theaquoeus phasewith CH
2Cl2 (3 ꢁ 50 mL), theorganic layre was
washed with brine (2 ꢁ 50 mL). The organic phase was dried over
MgSO4, filtered off and concentrated. Aldehyde (4) was isolated as a
yellow oil after purification by flash-chromatography on silica (eluent:
hexanes/AcOEt: 90/10).
3-( p-Methylphenyl)propenal (4b, R5CH3)[31]: 3.58 g (80% yield).
1H-NMR (300 MHz, CDCl3): ꢀ 2.42 (3H, s), 6.68 (1H, d, J ¼ 16.6 Hz),

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Chuzel and Piva
7.26 (2H, d, J ¼ 7.9 Hz), 7.47 (1H, d, J ¼ 16.6 Hz), 7.49 (2H, d,
J ¼ 7.9 Hz), 9.72 (1H, s). IR: ꢁ ¼ 3028, 2987, 2922, 2816, 2735, 1682,
1627, 1609, 1569, 1513, 1451, 1292, 1254, 1182, 1125, 973 cmÀ1
.
3-( p-Bromophenyl)propenal (4c, R5Br)[32]
: 4.12 g (70% yield).
1H-NMR (300 MHz, CDCl3): ꢀ 6.74 (1H, d, J ¼ 16.0 Hz), 7.44 (1H, d,
J ¼ 16.4 Hz), 7.45 (2H, d, J ¼ 8.3 Hz), 7.60 (2H, d, J ¼ 8.5 Hz), 9.74 (1H, s).
IR: ꢁ ¼ 3047, 2992, 2825, 2742, 1678, 1625, 1584, 1490, 1409, 1389, 1301,
1252, 1129, 1074, 1009, 981 cmÀ1
.
3-( p-Methoxyphenyl)propenal (4d, R5OCH3)[31]: 70%. 1H-NMR
(300 MHz, CDCl3): ꢀ 3.88 (3H, s), 6.65 (1H, d, J ¼ 15.8 Hz), 6.97 (2H,
d, J ¼ 8.9 Hz), 7.45 (1H, d, J ¼ 15.8 Hz), 7.55 (2H, d, J ¼ 8.9 Hz), 9.69
(1H, s). IR: ꢁ ¼ 3033, 2981, 2939, 2843, 2765, 1673, 1621, 1601, 1571,
1512, 1462, 1308, 1263, 1175, 1130, 977 cmÀ1
.
General Procedure for Tandem
Michael–Wittig–Horner Reaction (5a–d)
In a 100 mL two-necked flask dried prior use, was placed copper
iodide (0.432 g, 2.25 mmol) in ether (25 mL). The solution was cooled
to 0ꢂC and a 1.6 M solution of methyllithium in hexane (2.8 mL,
4.50 mmol) was carefully added. After 40 min at this temperature, the
colorless solution was cooled to À78ꢂC and aldehyde (4) (2.25 mmol)
was added dropwise. The dark yellow resulting mixture was stirred for
2.5 h while the temperature reached À15ꢂC. Phosphonate( 2) (0.9 mL,
4.50 mmol) dissolved in ether (1 mL) was added. The solution was stirred
overnight, then hydrolysed with a saturated solution of ammonium
chloride (25 mL). The crude solution was extracted with ether
(3 ꢁ 25 mL), dried over MgSO4, filtered and concentrated. The pure
compound (5) was obtained after flash-chromatography on silica
(eluent: hexanes/ethyl acetate: 97/3).
Ethyl 5-phenyl-hexen-2-oate (5a, R5H)[33]: 0.235 g (48% yield).
1H-NMR (300 MHz, CDCl3): ꢀ 1.12 (3H, t, J ¼ 7.1 Hz), 1.20 (3H, d,
J ¼ 7.0 Hz), 2.45 (2H, m), 2.82 (1H, m), 4.08 (2H, q, J ¼ 7.1 Hz), 5.72
(1H, d, J ¼ 15.4 Hz), 6.80 (1H, m), 7.13 (5H, m). 13C-NMR (75 MHz,
CDCl3): ꢀ 14.3, 22.0, 37.0, 39.9, 59.8, 120.5, 126.2, 127.0, 128.5, 146.3,
148.6, 166.4. IR: ꢁ ¼ 3028, 2963, 2930, 1717, 1654, 1603, 1494, 1453, 1368,
1307, 1268, 1229, 1203, 1166, 1045, 844 cmÀ1
.
Ethyl 5-( p-methylphenyl)-hexen-2-oate (5b, R5CH3)[20]: 0.245 g
1
(47% yield). H-NMR (300 MHz, CDCl3): ꢀ 1.18 (3H, d, J ¼ 7.1 Hz),
1.19 (3H, t, J ¼ 7.1 Hz), 2.25 (3H, s), 2.35 (2H, m), 2.79 (1H, m), 4.09

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Tandem Michael–Wittig–Horner Reaction
399
(2H, q, J ¼ 7.2 Hz), 5.72 (1H, d, J ¼ 15.6 Hz), 6.80 (1H, m), 7.25 (4H, m).
13C-NMR (75 MHz, CDCl3): ꢀ 14.6, 21.4, 22.1, 39.1, 41.4, 60.5, 123.0,
127.1, 129.6, 136.1, 143.5, 147.9, 166.9. IR: ꢁ ¼ 3039, 2973, 1715, 1626,
1605, 1581, 1520, 1469, 1371, 1305, 1264, 1180, 1146, 1037, 849 cmÀ1
.
Ethyl 5-( p-bromophenyl)-hexen-2-oate (5c, R5Br): 0.080 g (12%
yield). 1H-NMR (300 MHz, CDCl3): ꢀ 1.27 (3H, d, J ¼ 7.6 Hz), 1.31
(3H, t, J ¼ 7.1 Hz), 2.46 (2H, m), 2.87 (1H, m), 4.25 (2H, q, J ¼ 7.1 Hz),
6.04 (1H, d, J ¼ 15.1 Hz), 7.34 (2H, d, J ¼ 8.3 Hz); 7.44 (1H, m), 7.51 (2H,
d, J ¼ 8.3 Hz). 13C-NMR (75 MHz, CDCl3): ꢀ 14.6, 21.4, 22.1, 39.1, 41.4,
60.6, 123.0, 127.1, 129.6, 136.1, 143.5, 147.9, 166.9. IR: ꢁ ¼ 3026, 2983,
2933, 1707, 1628, 1586, 1488, 1403, 1369, 1312, 1274, 1242, 1174, 1135,
1073, 849 cmÀ1. MS: 296 (Mþ), 211, 185, 104.
Ethyl 5-( p-methoxyphenyl)-hexen-2-oate (5d, R5OCH3): 0.223 g
1
(40% yield). H-NMR (300 MHz, CDCl3): ꢀ 1.28 (3H, d, J ¼ 7.2 Hz),
1.30 (3H, t, J ¼ 7.2 Hz), 2.45 (2H, m), 2.87 (1H, dt, J ¼ 6.9 and 7.0 Hz),
3.81 (3H, s), 4.19 (2H, q, J ¼ 7.1 Hz), 5.80 (1H, d, J ¼ 15.6 Hz), 6.86 (2H,
d, J ¼ 8.6 Hz), 6.89 (1H, m), 7.12 (2H, d, J ¼ 8.6 Hz). 13C-NMR (75 MHz,
CDCl3): ꢀ 14.7, 21.4, 22.1, 39.1, 41.4, 60.5, 123.0, 127.1, 129.6, 136.2,
143.5, 147.9, 166.9. IR: ꢁ ¼ 3031, 2960, 2837, 1712, 1626, 1601, 1575,
1514, 1463, 1367, 1302, 1254, 1176, 1133, 1035, 831 cmÀ1. MS: 248
(Mþꢃ, 2), 135 (100), 105 (16), 91 (17), 68 (24).
General Procedure for Conversion of Unsaturated
Esters to Allylic Alcohols (7a–d)
In a 100 mL two-necked flask was placed ester (5) (2.20 mmol) in
ether (40 mL). After cooling to 0ꢂC, a 1.0 M ethereal solution of
methyl Grignard (5.0 mL) was added. The resulting solution was stirred
at r.t. overnight and carefully hydrolysed with an aqueous saturated
solution of NH4Cl (25 mL). After extraction with ether (3 ꢁ 25 mL), the
organic layers were collected, dried over MgSO4, filtered over a pad of
CeliteÕ and concentrated under vacuo. Alcohol (7) was purified by flash-
chromatography over silica (eluent: AcOEt/hexanes: 8/92).
(E )-2-Methyl, 6-phenyl 3-hepten-2-ol (7a, R5H): 0.180 g (40% yield).
(300 MHz, CDCl3): ꢀ 1.18 (6H, s), 1.19 (3H, d), 1.30 (m, OH), 2.21 (2H,
m), 2.69 (1H, m), 5.45 (2H, m), 7.16 (5H, m). 13C-NMR (75 MHz,
CDCl3): ꢀ 21.72, 30.1, 40.4, 41.5, 71.0, 126.4, 125.6, 127.5, 128.9, 140.1,
147.4. IR: ꢁ ¼ 3378, 3027, 2969, 2927, 1667, 1602, 1583, 1494, 1452, 1375,
1306, 1232, 1191, 1148, 971, 760, 692 cmÀ1. MS: 204 (Mþ, <1), 188 (15),
187 (100), 105 (41).

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Chuzel and Piva
(E )-2-Methyl, 6-( p-methyl)phenyl 3-hepten-2-ol (7b, R5CH3)[34]
:
1
0.394 g (82% yield). H-NMR (300 MHz, CDCl3): ꢀ 1.18 (3H, d), 1.19
(6H, s), 1.51 (m, OH), 2.19 (2H, m), 2.24 (3H, s), 2.66 (1H, m), 5.47 (2H,
m), 7.01 (4H, m). 13C-NMR (75 MHz, CDCl3): ꢀ 21.4, 21.8, 30.1, 39.9,
41.5, 71.0, 125.9, 127.3, 129.3, 135.7, 140.0, 144.4. IR: ꢁ ¼ 3378, 3020,
2970, 2925, 2872, 1577, 1515, 1455, 1415, 1374, 1308, 1233, 1150, 971,
816 cmÀ1. MS: 218 (Mþ, <5), 203, 200, 188, 131, 119, 118, 105, 91.
(E )-2-Methyl, 6-( p-bromo)phenyl 3-hepten-2-ol (7c): 0.249 g (50%
yield). 1H-NMR (300 MHz, CDCl3): ꢀ 1.25 (3H, d, J ¼ 7.7 Hz), 1.27
(6H, s), 1.58 (m, OH), 2.27 (2H, m), 2.76 (1H, m), 5.52 (2H, m), 7.07
(2H, d, J ¼ 8.5 Hz), 7.42 (2H, d, J ¼ 8.3 Hz). 13C-NMR (75 MHz, CDCl3):
ꢀ 21.6, 30.2, 39.9, 41.2, 71.0, 119.9, 125.1, 129.2, 131.7, 140.4, 146.3. IR:
ꢁ ¼ 3388, 3023, 2926, 1660, 1590, 1489, 1456, 1405, 1374, 1231, 1149,
1074, 1010, 971, 822 cmÀ1. MS: 283 and 281 (Mþꢃ, <2), 267 and 265
(M À H2O, 100), 185 and 183 (60).
(E )-2-Methyl, 6-( p-methoxy)phenyl 3-hepten-2-ol (7d): 0.207 g (40%
yield). 1H-NMR (300 MHz, CDCl3): ꢀ 1.15 (3H, d, J ¼ 7.0 Hz), 1.19 (6H,
s), 1.28 (1H, OH), 2.18 (2H, m), 2.65 (1H, m), 3.71 (3H, s), 5.46 (2H, m),
6.76 (2H, d, J ¼ 8.6 Hz), 7.02 (2H, d, J ¼ 8.6 Hz). 13C-NMR (75 MHz,
CDCl3): ꢀ 21.9, 30.1, 39.5, 41.6, 55.6, 71.0, 114.0, 125.8, 128.3, 139.5,
140.0, 158.1. IR: ꢁ ¼ 3399, 3028, 2967, 2928, 2836, 1611, 1583, 1520,
1458, 1441, 1374, 1302, 1246, 1178, 1036, 971, 830 cmÀ1
.
(E )-6-( p-Methoxyphenyl)-2-methyl-1,3-heptadiene (8d): 0.048 g (10%
yield). 1H-NMR (300 MHz, CDCl3): ꢀ 1.15 (3H, d, J ¼ 7.0 Hz), 1.71 (3H,
s), 2.15–2.38 (2H, m), 2.68 (1H, dt, J ¼ 7.0 Hz), 3.72 (3H, s), 4.48 (2H, s),
5.47 (1H, dt, J ¼ 15.6 and 7.1 Hz), 6.05 (1H, d, J ¼ 15.6 Hz), 6.77 (2H, d,
J ¼ 8.6 Hz), 7.04 (2H, d, J ¼ 8.6 Hz). 13C-NMR (75 MHz, CDCl3): ꢀ 19.0,
21.9, 39.7, 42.3, 55.6, 114.0, 114.8, 128.1, 129.5, 134.5, 139.6, 142.5, 158.1.
IR: ꢁ ¼ 2927, 1610, 1584, 1512, 1458, 1441, 1374, 1247, 1178, 1115.
Direct Conversion of (7b) to (1)-ar-Turmerone (9)
2
A solution of alcohol (7b) (0.200 g, 0.70 mmol) in CH2Cl2 was added
to a solution of PCC (0.45 g, 2.05 mmol) in thesamesolvent (20 mL) and
the reaction mixture was stirred overnight at r.t. After addition of Et2O
(30 mL), the resulting suspension was filtered over CeliteÕ and thefiltrate
was concentrated under vacuo. Compound (9) (0.047 g, 0.21 mmol) was
isolated by flash-chromatography (eluent: AcOEt/hexanes: 97/3). 31%.
1H-NMR (300 MHz, CDCl3): ꢀ 1.17 (3H, d, J ¼ 7.0 Hz), 1.78 (3H, s), 2.04
(3H, s), 2.24 (3H, s), 2.59 (2H, m), 3.22 (1H, m), 5.95 (1H, s), 7.03

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Tandem Michael–Wittig–Horner Reaction
401
(4H, m). 13C-NMR (75 MHz, CDCl3): ꢀ 21.7, 30.1, 40.4, 41.5, 71.0, 126.4,
125.6, 127.4, 128.9, 140.1, 147.4. IR: ꢁ ¼ 3020, 2962, 2925, 1686, 1620,
1515, 1446, 1378, 1358, 1309, 1260, 1111, 1036, 1012 cmÀ1
.
ACKNOWLEDGMENTS
C.N.R.S. and Region Rhone-Alpes are gratefully acknowledged
for financial support (AIP 1999–2001 and Programme Emergence,
respectively).
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Received in the Netherlands January 21, 2002