Preparation of 4-arylcyclopentenes by sequential diallylation of arylaldehydes and ring-closing metathesis

Article abstract of DOI:10.1081/SCC-200063971

Allylsilane diallylation of aryl aldehydes followed by ring closure metathesis leads to 4-arylcyclopentenes in good yields. Copyright Taylor & Francis, Inc.

Full text of DOI:10.1081/SCC-200063971

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Preparation of
4‐Arylcyclopentenes by
Sequential Diallylation of
Arylaldehydes and Ring‐Closing
Metathesis
Anne‐Catherine Durand a , Lamia Brahmi b , Mokhtar
Lahrech b , Salih Hacini b & Maurice Santelli a
a Laboratoire de Synthèse Organique , UMR 6180
CNRS and Université Paul Cézanne (Aix‐Marseille III):
Chirotechnologies: Catalyse et biocatalyse, Faculté
de St‐Jérôme , Marseille, France
b Laboratoire de Synthèse Organique , Université
d'Oran Es Sénia , Oran, Algeria
Published online: 15 Aug 2006.
To cite this article: Anne‐Catherine Durand , Lamia Brahmi , Mokhtar Lahrech , Salih
Hacini & Maurice Santelli (2005) Preparation of 4‐Arylcyclopentenes by Sequential
Diallylation of Arylaldehydes and Ring‐Closing Metathesis, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry,
35:13, 1825-1833, DOI: 10.1081/SCC-200063971
To link to this article: http://dx.doi.org/10.1081/SCC-200063971
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Synthetic Communicationsw, 35: 1825–1833, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200063971
Preparation of 4-Arylcyclopentenes by
Sequential Diallylation of Arylaldehydes
and Ring-Closing Metathesis
Anne-Catherine Durand
` ´
Laboratoire de Synthese Organique, UMR 6180 CNRS and Universite
´
Paul Cezanne (Aix-Marseille III): Chirotechnologies: Catalyse et
´ ´ ˆ
biocatalyse, Faculte de St-Jerome, Marseille, France
Lamia Brahmi, Mokhtar Lahrech, and Salih Hacini
´
` ´
Laboratoire de Synthese Organique, Universite d’Oran Es Senia,
Oran, Algeria
Maurice Santelli
Laboratoire de Synthese Organique, UMR 6180 CNRS and Universite
´
Paul Cezanne (Aix-Marseille III): Chirotechnologies: Catalyse et
`
´
´ ´ ˆ
biocatalyse, Faculte de St-Jerome, Marseille, France
Abstract: Allylsilane diallylation of aryl aldehydes followed by ring closure meta-
thesis leads to 4-arylcyclopentenes in good yields.
Keywords: Aldehydes, allylation, cyclization, cyclopentenes, metathesis
The formation of five-membered carbocycles has been intensely studied in
recent years[1] and, in particular, substituted cyclopentenes, such as 4-aryl-
cyclopentenes 3, are important building blocks used in organic synthesis. These
compounds have seldom been prepared and usualy as by-products in the
Received in Poland February 4, 2005
Address correspondence to Maurice Santelli, Laboratoire de Synthese Organique,
´ ´
UMR 6180 CNRS and Universite Paul Cezanne (Aix-Marseille III):
`
´
´ ˆ
Chirotechnologies: Catalyse et biocatalyse, Faculte de St-Jerome, Avenue Escadrille
Normandie-Niemen, 13397, Marseille Cedex 20, France. Fax: þ(33)491983865;
E-mail: m.santelli@univ.u-3mrs.fr
1825

1826
A.-C. Durand et al.
course of the Heck reaction of halobenzenes with cyclopentene.[2] Compound
3 can be subjected to a wide variety of additional chemical transformations
to give potential intermediates as cyclopentadienes and precursors for the
synthesis of natural products and biologically active compounds.
As part of our research program on allylsilane chemistry [preparation of
1-aryl-2,5-divinylcyclopentanes by double allylation of aryl aldehydes or cor-
responding acetals with 1,8-bis(trimethylsilyl)-2,6-octadiene (BISTRO)],[3]
we report herein the diallylation of aryl aldehydes followed by a ring-
closure metathesis.
Titanium tetrachloride–mediated double allylation reaction of p-anisal-
dehyde has been observed by Albaugh–Robertson and Katzenellenbogen[4]
and some years after, Mayr and Gorath showed that the formation of the
2 þ 1 product takes place when 2 equiv. of allylsilane per mol of benzal-
dehyde dimethyl acetal are used.[5]
We have observed that benzaldehyde, naphthaldehydes, and benzal-
dehydes substituted by electron-donor groups twice undergo allylation by
treatment with allylsilane and titanium tetrachloride, giving rise to 1,6-
heptadien-4-yl-substituted arene compounds 2 (Scheme 1 and Table 1). The
diallylation of phthalaldehyde leads to 2j, resulting from a single allylation
of each carbonyl moiety in modest yield. This moderate yield may be
explained by the instability in a reaction conditions of the product.
Having the required precursors in hand, we attempted the cyclisation by
ring-closing metathesis.[6] The reaction occurs smoothly, giving rise to 4-aryl
cyclopentenes 3 in good yields by using Grubbs’s first-generation ruthenium
catalyst (PCy3)2(Cl)2Ru ¼ CHPh.[7] In the case of 2h and 2i, only aryl cyclo-
pentenes 3h and 3i, respectively, are obtained in spite of the possibility of
formation of 3-oxaoctene derivatives. Finally, the isobenzofurane 2j gave
almost no product formation.
EXPERIMENTAL
1
CH2Cl2 was distilled on P2O5. All reactions were run under argon. H NMR
(300 MHz) and 13C NMR (75 MHz) spectra were recorded in a CDCl3
solution. Chemical shifts (d) are reported in ppm relative to CDCl3.
Scheme 1.

4-Arylcyclopentenes
1827
Table 1. Synthesis of 4-arylcyclopentenes
Entry
1
Yield of 2 (%)
Yield of 3 (%)
74
80
a
85
85
95
85
88
88
85
93
92
74
b
c
d
e
f
75
35
89
75
g
h
76
80
—
i
30
j

1828
A.-C. Durand et al.
Double Allylation of Aryl Aldehydes, Typical Procedure
A flame-dried, three-necked, round-bottomed flask equipped with a magnetic
stirring bar, a thermometer, and an argon outlet was charged with anhydrous
CH2Cl2 (20 mL) and MeNO2 (1.2 mL, 20 mmol). The solution was cooled at
260 8C and TiCl4 (1 mL, 8.1 mmol) and then aldehyde (5.0 mmol) in
CH2Cl2 (2 mL) were added. After 15 min of stirring, the mixture was cooled
at 290 8C and allyltrimethylsilane (2.4 mL, 15 mmol, 3 equiv.) in CH2Cl2
(2 mL) was slowly added. The mixture was stirred at 285 8C for 3 h and
then warmed to 260 8C. After completion of the reaction (TLC; 5–15 h),
the mixture was poured into a saturated solution of NH4Cl. After the usual
workup, the crude product was purified by flash chromatography on silica
gel (petroleum ether then petroleum ether–ether 25 : 1).
4-Phenyl-1,6-heptadiene, 2a.[8] According to the general procedure with
;
benzaldehyde. 2a, colorless oil; IR 3062, 1640, 838 cm21 1H NMR
(CDCl3, 300 MHz) d7.38–7.21 (5H, m), 5.74 (2H, ddt, J ¼ 17.2, 10.2,
7.0 Hz), 5.04 (2H, br d, J ¼ 17.2 Hz), 4.93 (2H, br d, J ¼ 10.4 Hz), 2.79
(1H, m), 2.45 (4H, m); 13C NMR (CDCl3, 75 MHz) d 144.8 (s), 136.9
(d)(2C), 128.4 (d)(2C), 127.9 (d)(2C), 126.2 (d), 116.2 (t)(2C), 45.7 (d),
40.4 (t)(2C); MS m/z 131 (100), 91 (50).
4-(p-Tolyl)-1,6-heptadiene, 2b.[9] According to the general procedure with
1
p-tolualdehyde. 2b, colorless oil; IR 3073, 1640, 911, 813 cm21; H NMR
(CDCl3, 300 MHz) d 8.21–7.08 (4H, m), 5.72 (2H, ddt, J ¼ 17.2, 10.2,
7.0 Hz), 5.04 (2H, br d, J ¼ 17.2 Hz), 4.93 (2H, br d, J ¼ 10.4 Hz), 2.74
(1H, m), 2.45 (4H, m), 2.37 (3H, s); 13C NMR (CDCl3, 75 MHz) d 141.7
(s), 137.1 (d)(2C), 135.6 (s), 129.1 (d)(2C), 127.7 (d)(2C), 116.1 (t)(2C),
45.3 (d), 40.5 (t)(2C), 21.2 (q); MS m/z 186 (3), 145 (100), 130 (15).
4-(p-Anisyl)-1,6-heptadiene, 2c.[5,10] According to the general procedure
with p-anisaldehyde. 2c, colorless oil; IR 3073, 1637, 1247, 1037, 912,
1
830 cm21; H NMR (CDCl3, 200 MHz) d 7.15 (2H, d, J ¼ 8.7), 6.91 (2H,
d, J ¼ 8.7 Hz), 5.75 (2H, ddt, J ¼ 17.0, 10.2, 6.9 Hz), 5.04 (2H, br d,
J ¼ 17.0 Hz), 5.01 (2H, br d, J ¼ 10.2 Hz), 3.84 (3H, s), 2.76 (1H, m), 2.44
(4H, m); 13C NMR (CDCl3, 50 MHz) d 158.0 (s), 137.0 (d)(2C), 136.7 (s),
128.6 (d)(2C), 116.1 (t)(2C), 113.7 (d)(2C), 55.2 (q), 44.8 (d), 40.6 (t)(2C);
MS m/z 161 (100), 146 (8), 119 (9), 91 (16).
4-(p-Bromophenyl)-1,6-heptadiene, 2d. According to the general procedure
1
with p-bromobenzaldehyde. 2d, colorless oil; IR 3073, 1640, 813 cm21; H
NMR (CDCl3, 300 MHz) d 7.37 (2H, d, J ¼ 8.3 Hz), 7.0 (2H, d,
J ¼ 8.3 Hz), 5.60 (2H, ddt, J ¼ 17.2, 10.4, 7.1 Hz), 4.95 (2H, br d,
J ¼ 17.2 Hz), 4.93 (2H, br d, J ¼ 10.4 Hz), 2.66 (1H, m), 2.31 (4H, m); 13C
NMR (CDCl3, 75 MHz) d 143.6 (s), 136.4 (d)(2C), 131.4 (d)(2C), 129.6

4-Arylcyclopentenes
1829
(d)(2C), 119.8 (s), 116.5 (t)(2C), 45.2 (d), 40.2 (t)(2C); MS m/z 211 (73), 209
(73), 130 (100) 129 (73). Anal. calcd. for C13H15Br: C, 62.17; H, 6.02. Found:
C, 62.25; H, 5.98.
1,4-bis(1,6-Heptadien-4-yl)benzene, 2e. According to the general procedure
with terephthalaldehyde (0.335 g, 2.5 mmol). 2e, pale yellow; IR 3045, 1647,
914, 839 cm21; 1H NMR (CDCl3, 300 MHz) d 7.24 (4H, br s), 5.74 (4H, ddt,
J ¼ 17.2, 10.0, 7.0 Hz), 5.04 (4H, br d, J ¼ 17.2 Hz), 5.00 (4H, br d,
J ¼ 10.0 Hz), 2.76 (2H, m), 2.46 (8H, m); 13C NMR (CDCl3, 75 MHz) d
142.4 (s)(2C), 137.0 (d)(4C), 127.6 (d)(4C), 116.0 (t)(4C), 45.3 (d)(2C),
40.4 (t)(4C); MS m/z 225 (64), 183 (90), 141 (100), 129 (32), 67 (43).
Anal. calcd. for C20H26: C, 90.16; H, 9.84. Found: C, 90.01; H, 9.78.
1-(1,6-Heptadien-4-yl)naphthalene, 2f. According to the general procedure
with 1-naphthaldehyde and 15 h at rt. 2f, pale yellow oil; IR 3047, 1639,
1
995, 910 cm21; H NMR (CDCl3, 300 MHz) d 8.20 (1H, d, J ¼ 8.3 Hz),
7.93 (1H, d, J ¼ 7.7 Hz), 7.79 (1H, d, J ¼ 8.3 Hz), 7.75 (4H, m), 5.79 (2H,
m), 5.10 (2H, d, J ¼ 18.0 Hz), 5.02 (2H, d, J ¼ 10 Hz), 3.77 (1H, t,
J ¼ 9.0 Hz), 2.64 (4H, m); 13C NMR (CDCl3, 75 MHz) d 140.6 (s), 136.8
(d)(2C), 134.1 (s), 132.1 (s), 129.1 (d), 126.7 (d), 125.9 (d), 125.5 (d),
125.4 (d), 123.8 (d), 123.3 (d), 116.5 (t)(2C), 39.6 (t)(2C), 38.9
(d)(br. signal); MS m/z 222 (27), 181 (100), 166 (29), 153 (11). Anal.
calcd. for C17H18: C, 91.84; H, 8.16. Found: C, 91.78; H, 8.21.
2-(1,6-Heptadien-4-yl)naphthalene, 2g. According to the general procedure
with 2-naphthaldehyde. 2g, colorless oil; IR 3052, 1639 cm21 1H NMR
;
(CDCl3, 300 MHz) d 7.85 (2H, m), 7.65 (s), 7.49 (2H, m), 7.39 (1H, m),
5.75 (2H, ddt, J ¼ 17.2, 10.1, 7.0 Hz), 5.06 (2H, br. d, J ¼ 17.2 Hz), 5.0
(2H, br. d, J ¼ 10.1 Hz), 2.96 (1H, quint., J ¼ 7.2 Hz), 2.54 (4H, m); 13C
NMR (CDCl3, 75 MHz) d 142.2 (s), 136.8 (d)(2C), 133.6 (s), 132.4 (s),
128.0 (d), 127.7 (d)(2C), 126.4 (d), 126.2 (d), 126.0 (d), 125.3 (d), 116.3
(t)(2C), 45.9 (d), 40.4 (t)(2C). Anal. calcd. for C17H18: C, 91.84; H, 8.16.
Found: C, 91.90; H, 8.18.
1-(1,6-Heptadien-4-yl)-2-allyloxybenzene, 2h. According to the general
1
procedure with 2-allyloxybenzaldehyde.[11] 2h, pale yellow oil; H NMR
(CDCl3, 300 MHz) d; 7.15 (2H, J ¼ 7.0 Hz), 6.96 (1H, d, J ¼ 7.4 Hz), 6.86
(1H, d, J ¼ 8.5 Hz), 6.09 (1H, ddt, J ¼ 17.2, 10.6, 4.9 Hz), 5.74 (2H, ddt,
J ¼ 17.2, 10.0, 7.0 Hz), 5.45 (1H, br. d, J ¼ 17.2 Hz), 5.29 (1H, br. d,
J ¼ 10.6 Hz), 5.00 (2H, br. d, J ¼ 17.2 Hz), 4.94 (1H, br. d, J ¼ 10.0 Hz),
4.55 (2H, br. d, J ¼ 4.9 Hz), 3.34 (1H, quint. J ¼ 7.1 Hz), 2.44 (4H, t,
J ¼ 7.1 Hz); 13C NMR (CDCl3, 75 MHz) d 156.4 (s), 137.4 (d)(2C), 133.7
(d), 133.1 (s), 128.1 (d), 126.9 (d), 120.7 (d), 116.9 (t), 115.8 (t)(2C), 112.0
(d), 68.9 (t), 38.8 (t)(2C), 37.8 (d). Anal. calcd. for C16H20O: C, 84.16;
H, 8.83. Found: C, 84.01; H, 8.78.

1830
A.-C. Durand et al.
1-(1,6-Heptadien-4-yl)-2-allyloxy-4-methoxybenzene, 2i. According to the
general procedure with 2-allyloxy-4-methoxybenzaldehyde.[12] 2i, pale
1
yellow oil; H NMR (CDCl3, 300 MHz) d 7.06 (1H, d, J ¼ 8.1 Hz), 6.50
(1H, d, J ¼ 8.1 Hz), 6.48 (1H, s), 6.09 (1H, m), 5.75 (2H, m), 5.47 (1H, br.
d, J ¼ 18.1 Hz), 5.30 (1H, br. d, J ¼ 10.2 Hz), 5.01 (2H, br. d, J ¼ 18.0 Hz),
4.96 (2H, br. d, J ¼ 11.3 Hz), 4.55 (2H, br. s), 3.80 (3H, s), 3.27 (1H,
quint., J ¼ 7.2 Hz), 2.44 (4H, br. t, J ¼ 7.2 Hz); 13C NMR (CDCl3,
75 MHz) d 158.8 (s), 157.2 (s), 137.4 (d)(2C), 133.5 (d), 128.3 (d), 125.4
(s), 116.9 (t), 115.7 (t)(2C), 104.3 (d), 99.8 (d), 68.8 (t), 55.2 (q), 38.9
(t)(2C), 37.4 (t). Anal. calcd. for C17H22O2: C, 79.03; H, 8.58. Found: C,
78.88; H, 8.65.
(R,S)-1,3-Diallyl-1,3-dihydro-isobenzofuran 2j.[13] According to the general
procedure with phthalaldehyde (0.335 g, 2.5 mmol) and 2 h at 260 8C.
1
Colorless oil; IR 3070, 1640, 1044, 994, 912, 753 cm21; H NMR (CDCl3,
300 MHz) d 7.31 (2H, m), 7.22 (2H, m), 5.89 (2H, ddt, J ¼ 17.3, 10.2,
6.9 Hz), 5.38 (2H, br. t, J ¼ 4.9 Hz), 5.17 (2H, br. d, J ¼ 17.3 Hz), 5.12
(2H, br. d, J ¼ 10.2 Hz), 2.63 (4H, m); 13C NMR (CDCl3, 75 MHz) d 141.9
(s), 134.1 (d), 127.5 (d), 121.4 (d), 117.7 (t), 82.5 (d), 41.1 (t); MS m/z 159
(100), 131 (92), 91 (27), 77 (9).
Preparation of Aryl Cyclopentenes, Typical Procedure
Diallyl derivatives 2 (5 mmol) in CH2Cl2 (50 mL) was stirred in presence
of (PCy3)2(Cl)2Ru ¼ CHPh (206 mg, 0.025 mmol, 0.05 equiv.). After com-
pletion of the reaction (TLC), the solvent was evaporated and the crude
product was purified by flash chromatography on silica gel (petroleum ether
then petroleum ether–ether 25 : 1).
4-Phenylcyclopentene 3a.[14] Precursor 2a was reacted as indicated in the
general procedure. 3a colorless oil; IR 3058, 3024, 1601, 836, 756 cm21
;
1H NMR (CDCl3, 300 MHz) d 7.38–7.22 (5H, m), 5.86 (2H, s), 3.54 (1H,
tt, J ¼ 9.1, 6.9 Hz), 2.90 (2H, dd, J ¼ 14.4, 9.1 Hz), 2.54 (2H, dd, J ¼ 14.4,
6.9 Hz); 13C NMR (CDCl3, 75 MHz) d 147.6 (s), 130.0 (d)(2C), 128.5
(d)(2C), 127.0 (d)(2C), 125.9 (d), 43.3 (d), 41.5 (t)(2C); MS m/z 144 (96),
129 (100).
4-p-Tolylcyclopentene, 3b. Colorless oil; IR 3049, 1613, 813 cm21; 1H NMR
(CDCl3, 300 MHz) d 7.20 (2H, ½AA0BB0, J ¼ 8.1 Hz), 7.15 (2H, ½AA0BB0,
J ¼ 8.1 Hz), 5.83 (2H, s), 3.48 (1H, tt, J ¼ 8.9, 7.0 Hz), 2.85 (2H, dd,
J ¼ 14.4, 8.9 Hz), 2.48 (2H, dd, J ¼ 14.4, 7.0 Hz), 2.37 (3H, s); 13C NMR
(CDCl3, 75 MHz) d 144.5 (s), 135.4 (s), 130.0 (d)(2C), 129.2 (d)(2C), 126.9
(d)(2C), 43.0 (d), 41.5 (t)(2C), 21.1 (q); MS m/z 158 (74), 143 (100), 128
(47). Anal. calcd. for C12H14: C, 91.08; H, 8.92. Found: C, 90.97; H, 8.85.

4-Arylcyclopentenes
1831
4-p-Anisylcyclopentene 3c.[14] Colorless oil; IR 3052, 1613, 1242, 1040,
1
826 cm21; H NMR (CDCl3, 300 MHz) d 7.20 (2H, ½AA0BB0, J ¼ 8.7 Hz),
6.86 (2H, ½AA0BB0, J ¼ 8.7 Hz), 5.79 (2H, s), 3.80 (3H, s), 3.44 (1H, tt,
J ¼ 8.9, 7.0 Hz), 2.82 (2H, dd, J ¼ 14.3, 8.9 Hz), 2.43 (2H, dd, J ¼ 14.3,
7.0 Hz); 13C NMR (CDCl3, 75 MHz) d 157.8 (s), 139.7 (s), 130.0 (d)(2C),
127.9 (d)(2C), 113.9 (d)(2C), 55.4 (q), 42.6 (d), 41.6 (t)(2C); MS m/z 174
(100), 159 (58), 144 (33).
4-(p-Bromophenyl)cyclopentene 3d. Colorless oil; IR 3052, 1072,
1
822 cm21; H NMR (CDCl3, 300 MHz) d 7.50 (2H, ½AA0BB0, J ¼ 8.3 Hz),
7.23 (2H, ½AA0BB0, J ¼ 8.3 Hz), 5.89 (2H, s), 3.52 (1H, tt, J ¼ 9.2,
6.5 Hz), 2.93 (2H, dd, J ¼ 14.2, 9.2 Hz), 2.50 (2H, dd, J ¼ 14.3, 8.9 Hz);
13C NMR (CDCl3, 75 MHz) d 146.6 (s), 131.5 (d)(2C), 129.8 (d)(2C), 128.7
(d)(2C), 119.5 (s), 42.6 (d), 41.3 (t); MS m/z 224 (69), 222 (74), 143 (100),
128 (83), 115 (31). Anal. calcd. for C11H11Br: C, 59.22; H, 4.97. Found: C,
59.33; H, 4.86.
1,4-bis(Cyclopent-3-enyl)benzene 3e. Colorless oil; IR 3052, 1618, 838,
1
700 cm21; H NMR (CDCl3, 300 MHz) d 7.24 (4H, s), 5.81 (4H, s), 3.50
(2H, tt, J ¼ 8.9, 7.2 Hz), 2.86 (4H, dd, J ¼ 14.4, 8.9 Hz), 2.50 (4H, dd,
J ¼ 14.4, 7.2 Hz); 13C NMR (CDCl3, 75 MHz) d 144.9 (s), 130.0 (d), 127.1
(d), 43.0 (d), 41.4 (t); MS m/z 210 (100), 143 (99), 128 (38), 115 (21).
Anal. calcd. for C16H18: C, 91.37; H, 8.63. Found: C, 91.43; H, 8.58.
4-(1-Naphthyl)cyclopentene 3f. Colorless oil; IR 3048, 1614, 1596, 777,
1
694 cm21; H NMR (CDCl3, 300 MHz) d 8.35 (1H, m), 8.11 (1H, m), 7.96
(1H, m), 7.73 (2H, m), 7.67 (2H, m), 6.14 (2H, s), 3.21 (1H, m), 3.21 (2H,
m), 2.94 (2H, m); 13C NMR (CDCl3, 75 MHz) d 142.8 (s), 134.3 (s), 131.8
(s), 130.0 (d), 129.0 (d), 126.6 (d), 125.6 (d)(2C), 125.4 (d), 123.9 (d),
123.4 (d), 40.7 (t), 39.1 (d); MS m/z 194 (100), 179 (19), 165 (19), 153 (9),
128 (6). Anal. calcd. for C15H14: C, 92.74; H, 7.26. Found: C, 92.68; H, 7.18.
4-(2-Naphthyl)cyclopentene 3g. Colorless oil; IR 3051, 1600, 852, 815,
1
744 cm21; H NMR (CDCl3, 300 MHz) d 7.87 (3H, m), 7.75 (1H, s), 7.50
(3H, m), 5.93 (2H, s), 3.72 (1H, tt, J ¼ 9.4, 6.7 Hz), 3.02 (2H, dd, J ¼ 14.7,
9.4 Hz), 2.66 (2H, dd, J ¼ 14.7, 6.7 Hz); 13C NMR (CDCl3, 75 MHz) d
145.0 (s), 133.7 (s), 132.2 (s), 130.0 (d)(2C), 128.3 (d), 127.7 (d), 125.95
(d), 125.9 (d), 125.2 (d), 125.0 (d), 43.4 (d), 41.5 (t); MS m/z 194 (100),
179 (45), 165 (19), 152 (11), 128 (29). Anal. calcd. for C15H14: C, 92.74;
H, 7.26. Found: C, 92.78; H, 7.22.
1-Allyloxy-2-(cyclopent-3-enyl)benzene 3h. Colorless oil; 1H NMR (CDCl3,
300 MHz) d 7.31–7.17 (2H, m), 6.98–6.87 (2H, m), 6.11 (1H, ddt, J ¼ 17.1,
10.6, 4.9), 5.86 (2H, m), 5.48 (1H, br. d, J ¼ 17.1 Hz), 5.31 (1H, br. d,
J ¼ 10.6 Hz), 4.59 (2H, dd, J ¼ 4.9, 1.5 Hz), 3.91 (1H, tt, J ¼ 9.1, 6.9 Hz),

1832
A.-C. Durand et al.
2.82 (2H, dd, J ¼ 14.3, 9.1 Hz), 2.53 (2H, dd, J ¼ 14.3, 6.9 Hz); 13C NMR
(CDCl3, 75 MHz) d 156.3 (s), 135.6 (s), 133.7 (d), 130.1 (d)(2C), 127.5 (d),
126.8 (d), 120.9 (d), 116.8 (t), 111.9 (d), 68.9 (t), 39.9 (t)(2C), 36.9 (d).
Anal. calcd. for C14H16O: C, 83.96; H, 8.05. Found: C, 84.02; H, 8.12.
2-Allyloxy-1-(cyclopent-3-enyl)-4-methoxybenzene 3i. Yellow oil; 1H NMR
(CDCl3, 300 MHz) d 7.12 (1H, d, J ¼ 8.8 Hz), 6.43 (2H, br. s), 6.04 (1H, ddt,
J ¼ 15.5, 10.6, 5.3 Hz), 5.76 (2H, s), 5.45 (1H, br. d, J ¼ 15.5Hz), 5.25 (1H,
br. d, J ¼ 10.6Hz), 4.52 (2H, d, J ¼ 5.3 Hz), 3.77 (3H, s), 2.72 (2H, dd,
J ¼ 14.2, 8.4 Hz), 2.42 (2H, dd, J ¼ 14.2, 7.0 Hz); 13C NMR (CDCl3,
75MHz) d 158.9 (s), 157.2 (s), 133.6 (d), 130.2 (d)(2C), 128.0 (s), 127.8 (d),
117.0 (t), 104.4 (d), 100.0 (d), 69.0 (t), 55.5 (q), 39.9 (t)(2C), 36.3 (d). Anal.
calcd. for C15H18O2: C, 78.23; H, 7.88. Found: C, 78.28; H, 7.78.
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