Allylsilane and diallylsilane reactions with functionalized ethylene ketals or benzodioxoles

Article abstract of DOI:10.1016/j.tet.2010.12.045

The bis-allylation of ethylene ketal and catechol ketal derivatives of 2,5-hexanedione occurred with a great stereoselectivity. The tetraallylation of bis-catechol ketal derivatives of 2,5-hexanedione and 2-methyl-1,3- cyclohexanedione or the diallylation of 4-phenylbutan-2-one derivatives arise in good yields and these compounds were suitable substrates for ring-closing metathesis leading to 4,4-dialkylcyclopentenes. Condensation of 1,8-bistrimethylsilyl-2,6-octadiene (Bistro) with 4-phenylbutan-2-one catechol ketal derivatives or 2-methylcyclohexan-1,3-dione mono catechol ketal afforded in good yields cyclic and tricyclic products 12 or 23, respectively.

Full text of DOI:10.1016/j.tet.2010.12.045

Tetrahedron 67 (2011) 1448e1455
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Tetrahedron
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Allylsilane and diallylsilane reactions with functionalized ethylene ketals
or benzodioxoles
*
Nicolas Galy, Delphine Moraleda, Maurice Santelli
ˇ
ꢀ
ꢀ
ꢀ
ꢀ
Laboratoire Chimie Provence, associe au CNRS no 6264, Universite d’Aix-Marseille, Faculte de St-Jerome, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 October 2010
Received in revised form 13 December 2010
Accepted 14 December 2010
Available online 21 December 2010
The bis-allylation of ethylene ketal and catechol ketal derivatives of 2,5-hexanedione occurred with
a great stereoselectivity. The tetraallylation of bis-catechol ketal derivatives of 2,5-hexanedione and
2-methyl-1,3-cyclohexanedione or the diallylation of 4-phenylbutan-2-one derivatives arise in good
yields and these compounds were suitable substrates for ring-closing metathesis leading to 4,4-di-
alkylcyclopentenes. Condensation of 1,8-bistrimethylsilyl-2,6-octadiene (Bistro) with 4-phenylbutan-2-
one catechol ketal derivatives or 2-methylcyclohexan-1,3-dione mono catechol ketal afforded in good
yields cyclic and tricyclic products 12 or 23, respectively.
Keywords:
Allylsilane
Diallylsilane
Ó 2011 Elsevier Ltd. All rights reserved.
Ethylene ketals
Benzodioxoles
Diastereoselectivity
1. Introduction
R1
The allylation of electrophilic reagents has gained in importance
since the development of the allylsilane chemistry from the seven-
ties.1 In particular, formation of homoallyl alkyls ethers by allylation
of acetals (Hosomi reaction) is well documented (Scheme 1).2,3
R2
A
SiMe3
SiMe3
R1
R2
O
O
TiCl4
SiMe3
+
R1
R2
TiCl4
NO2Me
CH2Cl2
R1 R2
O
O
O
R1
SiMe3
+
OH
B
R2
CH2Cl2
1
Scheme 1. Reaction of allyltrimethylsilane with ethylene ketals (Hosomi reaction).
R1
R2
Scheme 2. Reaction of Bistro 1 with ethylene ketals.
C
For about fifteen years, we have developed the use of 1,8-bis
(trimethylsilyl)-2,6-octadiene (Bistro) 1 as nucleophilic reagent.4 In
the course of the titanium tetrachloride mediated reaction of Bistro
with an ethylene ketal, three products could be obtained, the very
interesting corresponding divinylcyclopentane A and two by-
product trienes B and C. Valuable yields of A have been observed
with benzylic ethylene ketals (R1¼Ph),5 but B and C were major
products with aliphatic ethylene ketals (Scheme 2).6
a benzylic cation could explain the formation of A. Increasing the
leaving group ability by using catechol ketals (2,2-di-
alkylbenzodioxoles) instead of ethylene ketals should enhance the
reactivity of the titanium specie (pKa of catechol, 9.45 and 12.8,7
9.31 and 12.49,8 9.21 and 11.0,9 9.20,10 9.34 and 12.6,11 glycol,
15.1)11 and therefore enhance its reactivity. The 13C NMR dis-
These results suggested that the titanium glycolate ether is not
enough leaving group to allow the substitution reaction with the
second allylsilane moiety. In the benzylic case, the formation of
placement of the functional carbon atom of catechol ketals (
118e125 ppm/TMS) was ∼10 ppm downfield compared to these of
ethylene ketals ( : 107e112 ppm/TMS).
d:
d
Indeed, the complex titanium dichloride catecholate D could be
more stable than its glycolate counterpart. The diallylation involved
* Corresponding author. E-mail address: m.santelli@univ-cezanne.fr (M. Santelli).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.12.045

N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
1449
the formation of the titanium complex, which underwent a sub-
stitution reaction by the second allylsilane moiety to release com-
plex D. This titanium complex is a stable, well known compound
(CAS number, 13523-46-1)(Scheme 3).12
making easier the release of chloride anions essential to the resti-
tution of the allylic moiety with rearrangement.19
−
)
Cl(
SiMe3
−
( )
Me3Si
Cl
TiCl4
SiMe3
El(+)
+
1
Me3Si
(+)
CH2Cl2
R1
R2
El
O
O
R1
R2
A
+
2 Me3SiCl
El
E
O
O
Scheme 6. Participation reaction in the course of the reaction of Bistro with an elec-
trophilic reagent in the absence of nitromethane.
Cl
Ti(IV )
O
Ti(IV )
+
Cl
O
D
Then, we investigated the reaction of allyltrimethylsilane and
Bistro with various ethylene and catechol ketals.
Scheme 3. Postulated reaction of Bistro with 2,2-dialkylbenzodioxoles.
From the synthetic point of view, it was very important to obtain
alcohols, which are more suitable for further manipulation than
homoallyl ethers. So we studied the reaction of allyltrimethylsilane
with the hexan-2,4-dione mono ethylene ketal 4, diethylene ketal
6, and dicatechol ketal 7. In each case, reactions gave rise to diols
resulting from a twice allylation. More interestingly, reactions are
The chemistry of 2,2-dialkylbenzodioxoles are weakly de-
veloped. Some results confirmed the easy substitution of the ether
linkage. In particular, treatment with boron tribromide exclusively
led to gem-dibromo derivatives in excellent yields,13 and the
dichloroalane provoked reductive opening to give phenolic
ethers.14
stereoselective, the hexan-2,4-dione mono ethylene ketal
4
affording mainly dl-5 while 6 and 7 gave rise to meso-5 (Scheme 7).
These results demonstrated that a stereo-cooperativity should oc-
cur between the two functional groups with, probably, the forma-
tion of TiCl4 mediated cyclic intermediates.17c,20a The only
comparable result deals with allylstannation of hexan-2,4-dione
with allyldibutyltin chloride in the presence of water, which led to
a 1:1 mixture of dl-5 and meso-5 (no yield given).21
2. Results and discussion
Consequently, we prepared various benzodioxoles15 to confirm
this hypothesis. With 2,2-dialkyl-1,3-benzodioxoles, we have re-
cently shown that allyltrimethylsilane cleanly reacts to give 4,4-
dialkylhepta-1,6-dienes resulting from
a
diallylation process
(Scheme 4).16
OH
S
TiCl4 (4 equiv.)
NO2Me (4 equiv.)
CH2Cl2
S
TiCl4
O
R1
O
R2
O
OH
4 equiv
R1 R2
MeNO2
dl
-5, 63%
SiMe3
3 equiv
+
O
O
SiMe3
CH2Cl2
OH
R
4
(3 equiv.)
S
Scheme 4. Diallylation of 2,2-dialkyl-1,3-benzodioxoles.
−
90 °C, 4 h
OH
meso-
meso-
5, 11%
Moreover, these 4,4-dialkylhepta-1,6-dienes can be used in the
ring-closing metathesis to give 4,4-dialkylcyclopentenes, as in the
following example from cyclopentanone (Scheme 5).
O
O
dito
5
, 54%
O
O
6
TiCl4
2 equiv
dito
meso-
5, 60%
SiMe3
3 equiv
+
O
O
MeNO2
CH2Cl2
O
O
TiCl4 (4 equiv.)
NO2Me (4 equiv.)
CH2Cl2
−
−
75 to 45 °C, 20 h
2
, 50 %
O
O
st
1
generation Grubb's catalyst
7
SiMe3
(12 equiv.)
3, 67%
−
75 °C, 48 h
8
, 72%
Scheme 5. Conversion of cyclopentanone catechol ketal to the doubly homologated
product 2 followed by ring-closing metathesis.
Scheme 7. Allylation of the 2,5-hexanedione derivatives.
In this preliminary report, the importance of the presence of
nitromethane (4 M equiv) was determining. This additive reduced
or prevented the formation of by-products E. It’s resulted from
a participation reaction of the second allylsilane moiety in the first
addition step of the electrophilic reagent El(þ) (Scheme 6).17,18 The
TiCl4 mediated dialkylation reaction of acyl chlorides or ethylene
ketals by Bistro is altered by the presence of a nitro group, either in
the co-solvent (nitromethane) or in the aliphatic chain. This effect
is due to a complexation between the nitro group and titanium,
Interestingly, the tetraallylation of the dicatechol ketal 7 giving
rise to 8 was performed in a very good yield to give only one
product by using a large excess of allyltrimethylsilane.
The structure of the tetraene 8 resulting from a tetraallylation is
confirmed by a ring-closing metathesis reaction using the ‘first-
generation’ Grubbs catalyst22 giving bis-cyclopentene 9 in good
yields (Scheme 8).

1450
N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
of 17a decreased to 25% and a new minor product, 20 (3%, only two
PCy3
Ru
PCy3
Cl
Cl
isomers, ∼60:40) appeared. Compound 20 came from a participa-
tion reaction of the second allylsilane moiety (product E) (Scheme
11). These results showed unambiguously the major role of nitro-
methane in this process. As in the previous results concerning the
reaction of Bistro with several aliphatic ethylene ketals,6 the major
isomer was the dl, and then the meso-anti.
Ph
(5 mol%)
CH Cl rt, 24 h
2
2,
9
, 85%
Scheme 8. Ring-closing metathesis reaction of 8.
The diallylation still occured with functionalized ketone cate-
chol ketals as 10a or 10b (Scheme 9). The ring-closing metathesis
afforded valuable cyclopentenes 12a and 12b in good yields.
R
TiCl4
10a
, R = H
+
1
10b, R = OMe
NO2Me
CH2Cl2
40 °C, 24 h
R
R
SiMe3
−
R
3 equiv
17a, R = H
O
O
TiCl4 (4 equiv)
17b
, R = OMe
17c, R = NO
O
O
2
MeNO2 (4 equiv)
CH2Cl2
18a
, R = H
18b, R = OMe
18c, R = NO
10a, R = H
10b
11a, R = H, 65%
11b
2
, R = OMe
, R = OMe, 61%
meso anti
-
meso syn
From 10a: 70% yield; ( )-17a :
From 10b: 57% yield; ( )-17b :
From 18a: 46% yield; ( )-17a :
From 18b: 41% yield; ( )-17b :
-17a :
-17b :
-17a :
-17b :
-
-17a = 63:23:14
-17b = 62:22:16
-17a = 66:23:11
-17b = 62:23:15
meso anti
meso syn
-
-
R
meso anti
-
meso syn
-
meso anti
meso syn
-
-
12a, R = H, 85%
meso anti
-
meso syn
-
18c
( ) 17c
-
-17c
-17c
From
: 42% yield;
:
:
= 62:23:15
12b
, R = OMe, 85%
Ph
Scheme 9. Diallylation reaction of 4-arylbutan-2-one derivatives 10a and 10b.
OH
+
OH
O
The diallylation of the dicatechol ketal 13 led to a mainly mix-
ture containing the product of tetrallylation 14 in 47% yield
(Scheme 10). Again, the structure was confirmed by a ring-closing
reaction producing 15 (75% yield, two isomers, syn and anti). Sur-
prisingly, we observed the formation of a cycloheptene ring instead
of a cyclopentene (Scheme 10). Indeed, the isomeric spiro[4.5]
decene 16 is slightly less stable than 15, at the B3LYP/G.311Gþþ
(d,p) level of the theory23 by dDG¼0.7 kcal/mol (for 15,
OH
SiMe3
Ph
19
20
Scheme 11. Reactions of Bistro 1 with 4-phenylbutan-2-one derivatives.
The structure of 19 was confirmed by a ring-closing metathesis
reaction22 giving cyclohexene 21 as only one isomer as revealed by
the 13C NMR spectrum (Scheme 12).
E¼ꢀ663.572032 a.u., ZPE¼0.388711 a.u.,
spiro isomer 16: E¼ꢀ663.570196 a.u., ZPE¼0.388289 a.u.,
G¼ꢀ663.226559 a.u.).
D
G¼ꢀ663.227682 a.u.; for
D
TiCl4 (4 equiv.)
NO2Me (4 equiv.)
CH2Cl2
PCy3
Cl
Ru
Cl
Ph
O
O
O
PCy3
(5 mol%)
HO
OH
19
CH2Cl2, rt, 24 h
O
SiMe3
Ph
Ph
21, 78%
(12 equiv.)
Scheme 12. Ring-closing metathesis reaction of 19.
−
75 °C, 48 h
13
14, 47%
Surprisingly, the reaction with 2-methylcyclohexan-1,3-dione
mono catechol ketal 22 stereoselectively afforded the tricyclic diol
23 (Scheme 13).
PCy3
Ru
PCy3
Cl
Cl
Ph
(5mol%)
The relative stereochemistry of 23 was assigned through ex-
14
CH Cl rt, 24 h
2
2,
tensive NMR analysis. To sum up, 1H (500 MHz) and 13C (125 MHz)
15
16
, 75%
OH
Scheme 10. Allylation of the bis-dioxole 13 and the ring-closing metathesis reaction.
H
Me
OH
The poor solubility of dicatechol ketal of the 1,4-cyclo-
hexanedione in both CH2Cl2 and CHCl3 at low temperature do not
allowed any reaction with allyltrimethylsilane.
With Bistro 1 as allylsilane reagent, the catechol ketal 10a, or the
ethylene ketal 18a of the 4-phenylbutan-2-one, or the same cor-
responding ketals of 4-p-anisylbutan-2-one 10b and 18b, provided
the expected 1,3-divinylcyclopentane derivatives 17 in fair yields
from 10a,b (along with 10a, 5% of diol 19) and moderate yields from
18a,b (Scheme 11). Without nitromethane and from 10a, the yield
TiCl4
O
1
+
23
, 40%
O
NO2Me
CH2Cl2
40 °C, 24 h
O
H
Me
OH
H
−
22
HO
H
H
Scheme 13. Reaction of Bistro 1 with 2-methylcyclohexan-1,3-dione mono catechol
ketal 22.

N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
1451
resonances were assigned from J-resolve, DEPT, COSYGP, HMBC,
HMQC gradient, NOESY (see Experimental section).
TiCl4
CO2Me
The formation of diols 5,19, and 23, instead of phenolic ethers, is
difficult to explain. This unexpected finding seemingly defies our
long understanding of the mechanism of allysilane substitution. A
careful study of various products of the reaction (in organic and
water phases) showed that the only phenolic compound present
was the catechol. Clearly, the formation of alcohol instead of
homoallyl ether involves a hydrolysis step. As phenoxy ethers are
stable compounds under reaction conditions, we consider the for-
mation of an intermediate product, which gives rise to an alcohol
during the work-up. In two experiments, we have obtained diol 23
even though the crude reaction mixture was added to a solution of
sodium methylate (excess) in anhydrous methanol instead of the
usual hydrolysis. Taking into account solvent properties of nitro-
methane,24e27 the catecholechlorotitanium complex may be
substituted to its aci-form with release of titanium dichloride cat-
echolate D to give nitronate.28
NO2Me
+
1
+
CH2Cl2
O
O
CO2Me
−
40 °C
60 h
25
, 50% yield
CO2Me
24
OH
O
OH
O
+
CO2Me
MeO2C
SiMe3
, 7%
O
26
27
, 5%
HO
Scheme 16. Reaction of Bistro with methyl acetylacetate catechol ketal 24.
Next, a cascade reaction induced by the addition of chlorine
anion to the silicon atom provoked a bicyclization beginning with
a nucleophilic attack on the internal carbon atom of the vinyl group
and its addition to the carbonyl group (pushepull mechanism).29
Then, the hydrolysis (or methanolysis) afforded alcohol (with
retention of configuration) and nitromethane (Scheme 14). Al-
though the acyclic alkyl nitronates are unstable,28 ethyl meth-
anenitronate is a known compound.30 In superacid solutions, the
methylation of nitromethane led to the corresponding onium ion.31
These results showed that the substitution of catecholate by the
aci-form of nitromethane depends on subtle structural parameters
(the increase of the concentration of nitromethane drastically re-
duced the reaction rate).
3. Conclusions
O
O
The use of dioxoles instead of ethylene ketals notably increased
the reactivity of the functional carbon atom and allowed the di-
allylation even with Bistro 1, the reactivity of which is strongly
reduced compared to the trimethylallylsilane.
TiCl4
1
O
O
O
O
iCl4
22
O
N
Me-NO2
O
O
TiCl4
O
4. Experimental section
4.1. General
O
O
Me3Si
−
Cl(
)
TiCl2
O
OTiCl
n
Me3Si
D
All reactions were performed under an argon atmosphere in
oven-dried glassware. CH2Cl2, was freshly distilled from P2O5.
Other reagents and solvents were obtained from commercial
sources and used as received. Flash column chromatography (FC):
Merck 230e400 mesh silica gel; EtOAc, Et2O, and petroleum ether
as eluents. Thin-layer chromatography (TLC): MachereyeNagel sil-
ica gel UV254 analytical plates; detection either with UV, or by
dipping in revealing solution. 1H and 13C NMR spectra were recor-
ded at 25 ꢁC in CDCl3 solutions at 500 or 300, and 1250 or 75 MHz,
respectively, using a Bruker Advance DPX 500 or AC300 spec-
O
HO
O TiCl
OH
n
N
O
H2O
+
Me-NO2
23
Scheme 14. Formation of tricyclic diol 23.
Previously, in the course of the Bistro addition to 2-acetylcy-
clohexanone mono ethylene ketal, a similar reaction giving a tri-
cyclic alcohol was observed, but in the last step an elimination of
glycolate occurred (Scheme 15).32
trometers. Chemical shift
d in parts per million relative to CDCl3
(signals for residual CHCl3 in the CDCl3: 7.24 ppm for 1H NMR and
77.16 ppm (central) for 13C NMR). Carbon-proton couplings were
determined by DEPT sequence experiments.
H
H
O
O
HO
TiCl4
O
+
+
4.2. Synthesis of ethylene ketals and dioxoles. General
procedure
1
O
NO2Me
CH2Cl2
O
OH
20%
30%
A 500 mL flask equipped with a DeaneStark apparatus was
charged with ketone (0.1 mol), ethylene glycol (31 g, 0.5 mol) or
catechol (16.5 g, 0.15 mol), camphor-10-sulfonic acid (1 g, 4.3 mmol),
and toluene (200 mL). The mixture was refluxing, and completion of
the reaction was followed by TLC. Then, for the preparation of eth-
ylene ketals, the solution was washed with saturated aqueous so-
lution of NaHCO3, and dried over MgSO4. For the preparation of
dioxoles, thesolutionwas stirredfor 2 hwith anhydrous K2CO3 (15 g)
Scheme 15. Reaction of Bistro with 2-acetylcyclohexanone mono ethylene ketal.
We next investigated the reactivity of methyl acetylacetate
catechol ketal 24, but, in this case, the main product 25 came from
an elimination reaction of catecholate. Minor compounds 26 and 27
appeared as only one stereoisomer according to the 13C NMR
spectra (Scheme 16).

1452
N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
and then filtered. The solvent was evaporated in vacuo, and the
residue was flash chromatographed on silica gel.
3H); 13C NMR (75 MHz, CDCl3):
125.8 (d), 109.7 (s), 64.8 (t), 41.1 (t), 33.3 (t), 24.0 (q).
d
¼142.2 (s), 128.4 (d), 128.35 (d),
4.2.1. Cyclopentanone catechol ketal (CAS number, 183-32-4). 1H
4.2.11. 4-Anisylbutan-2-one ethylene ketal (18b) (CAS number,
NMR (300 MHz, CDCl3):
d
¼6.86e6.77 (m, 4H), 2.19e2.11 (m, 4H),
290309-44-3). 1H NMR (300 MHz, CDCl3):
d
¼7.10 (d, J¼8.7 Hz, 2H),
6.81 (d, J¼8.7 Hz, 2H), 3.95 (m, 4H), 3.76 (s, 3H), 2.65 (m, 2H), 1.91
(m, 2H), 1.35 (s, 3H); 13C NMR (75 MHz, CDCl3):
1.92e1.85 (m, 4H); 13C NMR (75 MHz, CDCl3):
d
¼147.50 (s), 125.43
(s), 121.09 (d) (2C), 108.27 (d) (2C), 37.16 (t) (2C), 23.41 (t) (2C).
d¼157.8 (s), 134.3
(s), 129.2 (d)(2C), 113.8 (d)(2C), 109.7 (s), 64.8 (t), 55.3 (q), 41.3 (t),
29.4 (t), 24.0 (q). C13H18O3 (222.28): C 78.24, H 8.16; found C 78.15,
H 8.21.
4.2.2. Hexan-2,5-dione mono ethylene ketal (4) (CAS number, 33528-
35-7). 1H NMR (300 MHz, CDCl3):
d
¼3.83e3.88 (m, 4H), 2.44 (t,
J¼7.5 Hz, 2H), 2.08 (s, 3H), 1.90 (t, J¼7.5 Hz, 2H), 1.24 (s, 3H); 13C
NMR (75 MHz, CDCl3):
(t), 30.0 (t), 24.0 (q).
d¼208.4 (s), 109.3 (s), 64.7 (t), 38.3 (q), 32.9
4.2.12. 4-(p-Nitrophenyl)butan-2-one ethylene ketal (18c)33
NMR (300 MHz, CDCl3):
¼8.11 (d, J¼8.7 Hz, 2H), 7.32 (d, J¼8.7 Hz,
2H), 3.99e3.93 (m, 4H), 2.83e2.77 (m, 2H), 2.00e1.94 (m, 2H), 1.34
(s, 3H); 13C NMR (CDCl3, 75 MHz)
150.3 (s), 146.3 (s), 129.2 (d)(2C),
.
1H
d
4.2.3. Hexan-2,5-dione bis-ethylene ketal (6) (CAS number, 944-26-
d
3). Mp 63 ꢁC; 1H NMR (300 MHz, CDCl3):
d
¼3.89 (br s, 8H), 1.7 (s,
123.7 (d)(2C), 109.3 (s), 64.9 (s)(2C), 40.4 (t), 30.2 (t), 24.1 (q).
4H), 1.27 (s, 6H); 13C NMR (75 MHz, CDCl3):
33.3 (t), 23.8 (q).
d
¼109.7 (s), 64.6 (t),
4.2.13. 2-Methyl-2-(methoxycarbonylmethyl)-1,3-benzodioxole (24)
(CAS number, 50836-24-3). 1H NMR (300 MHz, CDCl3):
d
¼6.77 (m,
4.2.4. 2,20-Dimethyl-2,20-ethylenebis(1,3-benzodioxole) (7) (CAS
number, 219787-12-9). Mp 121 ꢁC; 1H NMR (300 MHz, CDCl3):
4H), 3.67 (s, 3H), 2.94 (s, 2H), 1.81 (s, 3H); 13C NMR (75 MHz, CDCl3):
d
¼168.8 (s), 146.9 (s), 121.6 (d), 115.6 (s), 108.8 (d), 52.0 (q), 43.7 (t),
d
¼6.77e6.72 (m, 4H), 2.14 (s, 4H), 1.61 (s, 6H); 13C NMR (75 MHz,
24.4 (q).
CDCl3):
d
¼147.5 (s), 121.2 (d), 118.3 (s), 108.5 (d), 32.8 (t), 24.8 (q).
4.3. Allylation of ethylene ketals and dioxoles. General
procedure
4.2.5. 2-Methyl-1,3-cyclohexanedione mono catechol ketal (22). Mp
73 ꢁC; 1H NMR (300 MHz, CDCl3):
d
¼6.72e6.78 (m, 4H), 2.93 (q,
J¼6.6 Hz, 1H), 2.50e2.58 (m, 1H), 2.31e2.40 (m, 2H), 2.02e2.17 (m,
A 50 mL three-necked flask equipped with a thermometer,
a septum cap, a magnetic stirring bar, and argon outlet was charged
with anhydrous CH2Cl2 (25 mL) and anhydrous nitromethane
(1.1 mL, 20 mmol). The solution was cooled to ꢀ60 ꢁC, and TiCl4 was
added (2.2 mL, 20 mmol) followed by the ethylene ketal or the
dioxole (5 mmol). Then, the solution was cooled to ꢀ90 ꢁC, and
allyltrimethylsilane (2.40 mL, 15 mmol for 5, or 9.6 mL, 60 mmol for
8 and 14) in anhydrous CH2Cl2 (10 mL). For 5, the solution was
stirred at ꢀ90 ꢁC for 4 h, and for 8 and 14, the solution was warmed
to ꢀ75 ꢁC for 48 h. The completion of the reaction was followed by
TLC. Then, the solution was poured onto aqueous saturated NH4Cl
solution and extracted with CH2Cl2. The extract was washed until
neutrality and possibly filtrated on CeliteÒ. The solution was dried
over MgSO4 and concentrated under vacuum. The residue was
purified by flash chromatography on silica gel, eluting with a gra-
dient of petroleum etherediethyl ether.
1H), 1.80e1.98 (m, 2H), 1.09 (d, J¼6.6 Hz, 3H); 13C NMR (75 MHz,
CDCl3):
d
¼207.0 (s), 147.6 (s), 147.3 (s), 121.5 (d), 119.8 (s), 108.5 (d),
108.2 (d), 54.4 (d), 40.0 (t), 34.6 (t), 19.2 (t), 6.6 (q). C13H14O3
(218.25): C 71.54, H 6.47; found C 71.65, H 6.31.
4.2.6. 2-Methyl-1,3-cyclohexanedione dicatechol ketal (13). After
completion of the reaction according to the general procedure, the
solution was stirred with pentane (250 mL) for 15 min. After set-
tling, the pentane phase was concentrated and the solid was
crystallized in a mixture pentaneediethyl ether to give 13 (65%). 13,
mp 76 ꢁC; 1H NMR (300 MHz, CDCl3):
d
¼6.85e6.89 (m, 2H),
6.78e6.81 (m, 6H), 2.52 (q, J¼6.7 Hz, 1H), 2.25e2.32 (m, 2H),
1.89e2.05 (m, 1H), 1.69e1.83 (m, 3H), 1.09 (d, J¼6.7 Hz, 3H); 13C
NMR (75 MHz, CDCl3):
121.2 (d), 118.5 (s), 108.7 (d), 108.1 (d), 47.3 (d), 34.9 (t), 17.8 (t), 5.2
(q). C19H18O4 (310.34): C 73.53, H 5.85; found C 73.55, H 5.81.
d
¼148.1 (s), 147.3 (s), 147.3 (s), 121.3 (d),
4.3.1. 1,1-Diallylcyclopentane (2) (CAS number, 1187741-04-3). Yield
4.2.7. 1,4-Cyclohexanedione dicatechol ketal. Mp 270 ꢁC; 1H NMR
50%; 1H NMR (300 MHz, CDCl3):
d
¼5.82 (ddt, J¼15.8, 11.2, 7.4 Hz,
(300 MHz, CDCl3):
CDCl3):
72.96, H 5.44; found C 73.05, H 5.38.
d
¼6.78 (br s, 8H), 2.21 (s, 8H); 13C NMR (75 MHz,
2H), 5.04 (br s, 2H), 5.02e4.98 (m, 2H), 2.06 (d, J¼7.5 Hz, 4H),
d
¼147.2 (s), 121.4 (d), 108.9 (d), 31.7 (t). C19H18O4 (310.34): C
1.65e1.55 (m, 4H), 1.45e1.37 (m, 4H); 13C NMR (75 MHz, CDCl3):
d
¼136.2 (d)(2C),116.8 (t)(2C), 45.2 (s), 43.6 (t)(2C), 36.9 (t)(2C), 24.9
(t)(2C).
4.2.8. 2-Methyl-(2-phenylethyl)-1,3-benzodioxole (10a). 1H NMR
(300 MHz, CDCl3):
d
¼7.26e7.36 (m, 5H), 6.85 (s, 4H), 2.84e2.89 (m,
4.3.2. (4R
*
,7R
*
)-4,7-dimethyl-1,9-decadien-4,7-diol
(dl-5)21. 1H
2H), 2.28e2.34 (m, 2H), 1.72 (s, 3H); 13C NMR (75 MHz, CDCl3):
NMR (300 MHz, CDCl3):
d
¼5.81e5.95 (m, 2H), 5.06e5.17 (m, 4H),
d
¼147.6 (s), 141.3 (s), 128.5 (d), 128.4 (d), 126.1 (d), 121.2 (d), 118.4
2.55 (½AB d, J¼14.1, 7.1 Hz, 1H), 2.48 (½AB d, J¼14.1, 7.1 Hz, 1H),
(s), 108.5 (d), 41.1 (t), 29.5 (t), 24.6 (q). C16H16O2 (240.30): C 79.97, H
6.71; found C 79.85, H 6.61.
1.84e1.99 (m, 4H), 1.51 (s, 6H); 13C NMR (75 MHz, CDCl3):
d¼133.4
(d), 119.1 (t), 72.6 (s), 48.7 (t), 48.6 (t), 38.6 (t), 29.8 (q).
4.2.9. 2-Methyl-[2-(p-anisyl)ethyl]-1,3-benzodioxole (10b). 1H NMR
4.3.3. (4R
*
,7S
)-4,7-dimethyl-1,9-decadien-4,7-diol (meso-5)21. 1H
*
(300 MHz, CDCl3):
(s, 4H), 3.80 (s, 3H), 2.84e2.75 (m, 2H), 2.30e2.22 (m, 2H), 1.69 (s,
3H); 13C NMR (75 MHz, CDCl3):
157.9 (s), 147.6 (s), 133.3 (s), 129.3
(d), 121.1 (d), 118.5 (s), 113.9 (d), 108.4 (d), 55.3 (q), 41.3 (t), 28.5 (t),
24.6 (q). C17H18O3 (270.32): C 75.53, H 6.71; found C 75.55, H 6.68.
d
7.15 (d, J¼8.6 Hz, 2H), 6.85 (d, J¼8.6 Hz, 2H), 6.82
NMR (300 MHz, CDCl3):
d
¼5.77e5.94 (2H, m), 5.06e5.13 (4H, m),
2.53 (1H, ½AB d, J¼14.1, 6.9 Hz), 2.46 (1H, ½AB d, J¼14.1, 7.1 Hz),
2.21 (2H, d, J¼7.5 Hz), 1.75e1.85 (2H, m), 1.58e1.65 (4H, m), 1.49
d
(3H, s),1.15 (3H, s); 13C NMR (75 MHz, CDCl3):
d
¼133.8 (d),133.6 (d),
119.1 (t), 118.8 (t), 73.2 (s), 71.9 (s), 48.5 (t), 46.4 (t), 37.8 (t), 36.3 (t),
29.8 (q), 26.9 (q).
4.2.10. 4-Phenylbutan-2-one ethylene ketal (18a) (CAS number,
69246-00-0). 1H NMR (300 MHz, CDCl3):
3.98e4.01 (m, 4H), 2.73e2.78 (m, 2H), 1.97e2.03 (m, 2H), 1.41 (s,
d
¼7.20e7.33 (m, 5H),
4.3.4. 4,7-Diallyl-4,7-dimethyldeca-1,9-diene (8). Yield 72% from 7;
1H NMR (300 MHz, CDCl3):
d¼5.85e5.70 (m, 4H), 5.05e4.95 (m,

N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
1453
8H), 2.10e1.90 (m, 8H), 1.60e1.00 (m, 4H), 0.8 (s, 6H); 13C NMR
(75 MHz, CDCl3):
(s) (2C), 32.3 (t) (2C), 24.8 (s) (2C). C18H30 (246.23): C 87.73, H 12.27;
found C 87.78, H 12.15.
1.70e1.40 (m, 4H), 1.06 (s, 0.63H), 0.91 (s, 1.9H), 0.72 (s, 0.48H); 13
C
d
¼135.4 (d) (4C), 117.1 (t) (4C), 44.0 (t) (4C), 35.8
NMR (75 MHz, CDCl3):
d¼151.7 (s), 146.3 (s), 140.6 (d), 139.9
(d),139.6 (d), 129.2 (d), 123.8 (d), 123.7 (d), 115.8 (t), 115.5 (t), 114.4
(t), 56.1 (d), 54.1 (d), 52.7 (d), 52.3 (d), 47.3 (s), 39.5 (t), 30.8 (t), 29.1
(t), 29.0 (t), 28.1 (t), 27.4 (t), 20.9 (q). C18H28NO2 (285.38): C 75.76, H
8.12; found: C 75.82, H 8.18.
4.3.5. 2,2-Diallyl-4-phenylbutane (11a). Yield 65% from 10a; 1H
NMR (300 MHz, CDCl3):
5.09e5.02 (m, 4H), 2.58e2.53 (m, 2H), 2.05 (d, J¼7.5 Hz, 4H),
1.53e1.47 (m, 2H), 0.93 (s, 3H); 13C NMR (75 MHz, CDCl3):
(s), 135.2 (d)(4C), 128.4 (d), 125.7 (d), 117.3 (t)(2C), 44.0 (t)(2C), 41.7
(t), 36.1 (s), 30.2 (t), 24.7 (q). C16H22 (214.35): C 89.65, H 10.35;
found C 89.79, H 10.25.
d
¼7.28e7.09 (m, 5H), 5.91e5.78 (m, 2H),
4.4.4. 3,8-Dimethyl-1,10-diphenyl-4,7-divinyldecan-3,6-diol
d¼143.4
(19). Yield 5% from 18a; 1H NMR (300 MHz, CDCl3):
d
¼7.1e7.3 (m,
10H), 5.5e5.85 (m, 2H), 4.9e5.25 (m, 4H), 2.6e2.8 (m, 2H),
2.0e2.07 (m, 2H), 1.70e1.82 (m, 1H), 1.30e1.65 (m, 3H), 1.20 (s, 3H),
1.15 (s, 3H), 0.85e0.95 (m, 2H); 13C NMR (75 MHz, CDCl3):
d
¼143.0
(s), 139.0 (d), 138.95 (d), 138.9 (d), 138.8 (d), 128.5 (d), 125.8 (d),
119.2 (t), 119.6 (t), 118.6 (t), 114.7 (t), 114.6 (t), 73.8 (s), 73.4 (s), 55.4
(d), 54.6 (d), 42.1 (t), 33.9 (t), 33.8 (t), 29.9 (t), 29.8 (t), 28.5 (t), 28.1
(t), 28.5 (t), 27.48 (t), 24.3 (q), 24.1 (q), 24.0 (q). C16H28O2 (252.21): C
76.14, H 11.18; found C 76.23, H 11.28.
4.3.6. 2,2-Diallyl-4-(4-p-methoxyphenyl)butane (11b). Yield 61%
from 10b; 1H NMR (300 MHz, CDCl3):
d
¼7.10 (d, J¼8.2 Hz, 2H), 6.84
(d, J¼8.2 Hz, 2H), 5.94e5.80 (m, 2H), 5.11e5.05 (m, 4H), 3.79 (s, 3H),
2.56e2.50 (m, 2H), 2.07 (d, J¼7.4 Hz, 4H), 1.53e1.47 (m, 2H), 0.95 (s,
3H); 13C NMR (75 MHz, CDCl3):
129.3 (d)(2C), 117.3 (t)(2C), 113.9 (d)(2C), 55.4 (q), 44.0 (t)(2C), 41.9
(t), 36.1 (s), 29.3 (t), 24.7 (q). C17H24O (244.37): C 83.55, H 9.90;
found C 83.70, H 9.78.
d
¼157.8 (s), 135.5 (s), 135.2 (d)(2C),
4.4.5. 2-(2-Hydroxyphenoxy)-4-phenyl-2-[2-(trimethylsilylmethyl)-
3-vinylcyclopentyl]butane (20). Yield 5% from 10a in the absence of
nitromethane; 1H NMR (300 MHz, CDCl3)(M, major isomer; m,
minor isomer):
1H), 5.07e4.95 (m, 4H), 2.80e2.55 (m, 4H), 1.0e0.85 (m, 4H), 0.12
(q, m), 0.05 (q, M); 13C NMR (75 MHz, CDCl3):
(2C), 140.5 (d), 128.5 (d)(4C), 125.8 (d)(2C), 114.8 (t, M), 113.1 (t, m),
75.7 (s, M), 75.0 (s, m), 59.2 (d, m), 55.4 (d, M), 51.8 (d, m), 49.1 (d,
M), 44.0 (t, M), 43.95 (t, m), 41.8 (d, m), 40.0 (d, M), 32.0 (t, m), 30.7
(t, M), 30.3 (t, m), 30.0 (t, M), 29.9 (t,M), 27.6 (t, m), 26.7 (t,M), 26.2
(t, m), 24.3 (q, m), 23.5 (q, M), 19.7 (t), 0.02 (q, m), ꢀ0.3 (q, M).
C27H38O2Si (422.26): C 76.72, H 9.06; found C 76.73, H 9.15.
d
¼7.35e7.15 (m, 9H), 5.85 (ddd, J¼17.1, 10.4, 8.2 Hz,
4.3.7. 2-Methyl-1,1,3,3-tetraallylcyclohexane (14). Yield 47% from
13; 1H NMR (300 MHz, CDCl3):
d
¼5.92e5.72 (m, 4H), 5.10e4.94 (m,
d¼143.1 (d), 142.9 (s)
8H), 2.22e1.78 (m, 8H),1.74e1.21 (m, 6H), 0.90 (d, J¼7.0 Hz, 3H); 13C
NMR (75 MHz, CDCl3):
d
¼135.2 (d)(4C), 117.0 (t)(4C), 47.1 (t)(2C),
44.4 (t)(2C), 41.3 (d), 37.1 (s)(2C), 31.4 (t)(2C), 22.2 (t), 8.1 (q). EI-MS:
m/z 217 (MþꢀC3H5), 175 (100), 161, 147, 135, 121, 107, 95.
4.4. Reaction of bistro with ethylene ketals and dioxoles.
General procedure
4.4.6. (1R
*
,2R
*
,5S
*
,6S
*
,8S
*
,12S
*
)-12-Methyl-5-vinyltricyclo[6.3.1.02,6]-
The same procedure that for the allylation is used with TiCl4
(2.2 mL, 20 mmol) followed by the ethylene ketal or the dioxole
(5 mmol). Then, the solution was cooled to ꢀ90 ꢁC, and Bistro 1
(3.17 g, 12.5 mmol) in anhydrous CH2Cl2 (10 mL) was added. For
cases of 17, 19, 20, and 23, the solution was warmed to ꢀ40 ꢁC for
24 h. For 25, 26, and 27, the solution was warmed to ꢀ40 ꢁC for 60 h.
dodecan-1,8-diol (23).
noe
15
H
Me
OH
12
8
H
5
7
9
4
11
3
1
6
2
13 14
10 HO
H
H
4.4.1. 2,5-Divinyl-1-methyl-1-(2-phenylethyl)cyclopentane
(17a). Yield 70% from 10a, and 46% from 18a; 1H NMR (300 MHz,
CDCl3):
d
¼7.17e7.37 (5H, m), 5.81e5.97 (2H, m), 4.90e5.17 (4H, m),
2.64e2.75 (2H, m), 2.45e2.49 (2H, m), 1.90e2.15 (2H, m), 1.50e1.72
Yield 40% from 22; 1H NMR (500 MHz, CDCl3):
d
¼5.75 (ddd, J¼17.1,
(4H, m), 1.10, 1.0, 0.75 (3H, s); 13C NMR (75 MHz, CDCl3)(ma: meso-
10.2, 9.8 Hz, H13), 4.91 (d, J¼17.1 Hz, H14), 4.85 (d, J¼10.2 Hz, H14),
2.32 (m, H6), 2.26 (m, H5), 2.21 (q, J¼7.1 Hz, H12), 2.15 (m, H2, H9),
1.93 (m, H4), 1.89 (m, H9), 1.86 (m, H3, H10), 1.85 (m, H7), 1.82 (m,
H11), 1.85 (m, H7), 1.64 (m, H3, H10), 1.40 (m, H4, H11), 1.18 (d,
anti; ms: meso-syn):
d¼143.7 (s, dl), 143.6 (s, ms), 140.6 (d, dl), 140.3
(d, dl), 139.9 (d, ms), 128.4 (d, dl), 125.6 (d, ms), 115.5 (t, ms), 115.1 (t,
dl), 114.2 (t, dl), 56.4 (d, ms), 54.1 (d, dl), 52.2 (d, dl), 52.1 (d, dl), 47.4
(s), 41.0 (t, ms), 39.8 (t), 30.8 (t, dl), 30.2 (t, ms), 29.0 (t, dl), 28.0 (t,
dl), 27.6 (t, ms), 23.9 (q, ma), 21.0 (q, dl), 15.5 (q, ms). C18H24 (240.19):
C 89.94, H 10.06; found C 89.85, H 10.01.
J¼7.1 Hz, Me15); 13C NMR (125 MHz, CDCl3):
¼142.9 (C13), 112.5
d
(C14), 77.1 (C8), 75.7 (C1), 52.3 (C5), 50.7 (C2), 48.6 (C7), 44.8 (C12),
44.0 (C6), 34.1 (C9), 33.4 (C11), 29.0 (C4), 26.5 (C3), 21.8 (C10), 9.6
(C15). C15H24O2 (236.18): C 76.23, H 10.24; found C 76.15, H 10.32.
4.4.2. 2,5-Divinyl-1-methyl-1-(2-p-anisylethyl)cyclopentane
(17b). Yield 57% from 10b, 41% from 18b; 1H NMR (300 MHz,
4.4.7. Methyl 3-methyl-4-ethylidenenona-2,8-dienoate (25). Yield
50% from 24; 1H NMR (300 MHz, CDCl3) (M, major isomer; m,
CDCl3):
d
¼7.15 (2H, d, J¼8.6 Hz), 6.83 (2H, d, J¼8.6 Hz), 5.70e5.98
(2H, m), 4.9e5.1 (4H, m), 3.78 (3H, s), 2.5e2.7 (m, 2H), 1.80e2.1 (2H,
m), 1.5e1.70 (6H, m), 1.07 (3H, s, ms), 0.93 (3H, s, dl), 0.72 (3H, s,
minor isomer):
d
5.71e5.78 (m, 1H), 5.26 (d, J¼8.5 Hz, 1H), 5.18 (d,
J¼8.8 Hz, 1H), 4.91 (d, J¼17.1 Hz, 1H), 4.82 (d, J¼10.1 Hz, 1H), 3.62 (s,
3H), 3.00 (s, 2H, m), 2.92 (s, 2H, M), 2.72e2.81 (m, 1H, M), 2.56 (q,
J¼7.2 Hz, 1H, m), 1.80e1.89 (m, 2H), 1.72 (s, 3H, m), 1.65 (s, 3H, M),
1.42e1.64 (m, 2H), 1.20e1.40 (m, 2H); 13C NMR (75 MHz, CDCl3):
ma); 13C NMR (75 MHz, CDCl3):
d
¼157.7 (s), 140.7 (d), 140.4 (d),
139.8 (d), 135.8 (s), 129.3 (d), 115.4 (t), 115.0 (t), 114.0 (t), 113.8 (d),
55.3 (q), 52.1 (d), 52.0 (d), 47.3 (s), 40.0 (t), 29.0 (t), 28.9 (t), 28.0 (t),
23.9 (q, ma), 20.9 (q, dl), 15.5 (q, ms). C19H26O (270.20): C 84.39, H
9.69; found C 84.11, H 9.78.
d
172.6 (s), 143.7 (d), 135.3 (t, M), 134.9 (d, m), 127.0 (s, M), 126.6 (s,
m),112.3 (t), 51.8 (d), 44.9 (t, M), 43.2 (q, M), 39.5 (t), 37.9 (t, m), 37.6
(q, m), 33.7 (t), 33.0 (t), 24.1 (q, m), 16.6 (q, M). C13H20O2 (208.15): C
74.96, H 9.68; found C 75.05, H 9.58.
4.4.3. 2,5-Divinyl-1-methyl-1-[2-p-nitrophenylethyl]cyclopentane
(17c). Yield 42% from 18c; 1H NMR (300 MHz, CDCl3):
J¼8.7 Hz, 2H), 7.26 (d, J¼8.7 Hz, 2H), 5.92e5.66 (m, 2H), 5.06e4.98
(m, 4H), 2.81e2.62 (m, 2H), 2.41e2.26 (m, 2H), 2.05e1.85 (m, 2H),
d
¼8.09 (d,
4.4.8. Methyl 3-methyl-3-(2-hydroxyphenoxy)-9-trimethylsilyl-4-vi-
nylnon-7-enoate (26). Yield 7% from 24; 1H NMR (300 MHz, CDCl3):

1454
N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
d
6.91e7.00 (m, 3H), 6.72 (t, J¼7 Hz, 1H), 5.40e5.60 (m, 2H),
major isomer); 13C NMR (75 MHz, CDCl3):
d
¼138.7 (d)(2C),129.2 (d)
5.05e5.28 (m, 3H), 3.74 (s, 3H), 2.89 (½AB, J¼15.9 Hz, 1H), 2.52
(½AB, J¼16.1 Hz, 1H), 2.08e2.15 (m, 2H), 1.90e1.98 (m, 1H),
1.41e1.50 (m, 2H), 1.24e1.33 (m, 1H), 1.16 (s, 3H), e0.01 (9H, s); 13C
(2C), 114.6 (t)(2C), 47.7 (t)(2C), 44.7 (s), 41.5 (t), 37.8 (t), 22.9 (t), 14.2
(q). EI-MS: m/z 230 (Mþ), 215, 201, 189, 173, 161, 147 (100), 133, 93.
NMR (75 MHz, CDCl3):
d
173.5 (s), 151.9 (s), 141.4 (s), 137.7 (d), 128.2
4.5.6. 3,6-Bis(2-hydroxy-4-phenyl-2-butyl)cyclohexene (21). Yield
(s), 126.8 (d), 126.5 (d), 125.1 (d), 123.3 (d), 119.7 (t), 119.2 (d), 116.2
(d), 83.4 (s), 53.5 (d), 52.3 (d), 40.0 (t), 27.9 (t), 27.8 (s), 25.0 (t), 20.8
(q), 18.8 (t), 1.6 (q). C22H34O4Si (390.22): C 67.65, H 8.77; found C
67.72, H 8.78.
78%; 1H NMR (300 MHz, CDCl3):
d
¼7.24e7.15 (m, 10H), 5.83 (br s,
2H), 2.74e2.66 (m, 4H), 2.34e2.25 (m, 2H), 1.97e1.72 (m, 10H), 1.24
(s, 3H), 1.17 (s, 3H); 13C NMR (75 MHz, CDCl3):
d
¼142.8 (s), 129.9 (d),
129.6 (d), 128.4 (d)(4C), 127.4 (d), 127.3 (d), 125.8 (d), 74.6 (s), 74.4
(s), 45.8 (d), 45.2 (d), 42.5 (t), 41.0 (t), 30.1 (t), 30.0 (t), 25.2 (t), 24.8
(d), 24.6 (t), 24.0 (t), 23.3 (d) 22.41 (t), 22.36 (t). C26H34O2 (378.26):
C 82.49, H 9.05; found C 82.55, H 9.15.
4.4.9. Dimethyl 3,6-di[3-(2-hydroxyphenoxy)-3-butyrate]-1,7-octa-
diene (27). Yield 5% from 24; 1H NMR (300 MHz, CDCl3):
d
6.92e6.96 (m, 4H), 8.38 (s, 2H, OH), 6.85 (dd, J¼8.1, 1.3 Hz, 2H),
6.73 (td, J¼9.1, 1.7 Hz, 2H), 5.72e5.83 (m, 2H), 4.89e5.01 (m, 4H),
3.73 (s, 6H), 2.84 (½AB, J¼15.7 Hz, 2H), 2.54 (½AB, J¼15.7 Hz, 2H),
2.29 (dd, J¼6.6, 2.5 Hz, 2H), 1.77e1.1.84 (m, 10H), 1.21 (s, 6H),
Acknowledgements
D.M. is grateful to the MEN for a grant and N.G. is grateful to the
ˇ
1.11e1.19 (m, 2H); 13C NMR (75 MHz, CDCl3):
d 173.8 (s), 151.9 (s),
ꢀ
CNRS and the Region Provence-Alpes-Cote d’Azur for a grant. We
143.9 (d), 141.4 (s), 124.9 (d), 123.3 (d), 119.1 (d), 116.2 (d), 112.3 (t),
84.2 (s), 52.2 (d), 47.1 (d), 41.7 (d), 40.0 (t), 32.6 (t), 32.3 (t), 27.9 (t),
26.5 (t), 20.3 (q). C30H38O8 (526.26): C 68.42, H 7.27; found C 68.52,
H 7.38.
thank Dr. R. Faure for the preparation of 2D NMR spectra and Dr. V.
Heran for mass analysis. This work has been financially supported
by the CNRS and the Ministere de l’Education Nationale. We are in-
debted to Dr. B. Vacher (Pierre Fabre Medicaments, Castres, Fr) for
ꢁ
ꢀ
helpful comments.
4.5. Ring-closing metathesis of diallyl derivatives. General
procedure
References and notes
In a 100 mL double-necked flask equipped with and argon outlet
was charged with anhydrous CH2Cl2, (80 mL), diallyl derivative
(0.4 mmol) 15 mg (0.02 mmol) of first generation Grubbs catalyst.
The solution was stirred for 24 h at room temperature. Then, the
solvent was removed under reduced pressure and the residue was
purified by chromatography on silica gel, eluting with n-pentane
(or petroleum ether/diethyl ether 80:20, for 21).
1. (a) Weber, W. P. Silicon Reagents for Organic Synthesis; Springer Verlag: Berlin,
1983; (b) Fleming, I.; Dunogues, J.; Smithers, R. Org. React. 1989, 37, 57e575;
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(c) Santelli, M.; Pons, J. M. Lewis Acids and Selectivity in Organic Synthesis; CRC:
Boca-Raton, 1995; (d) Yamamoto, H. Lewis Acids Reagents; Oxford Univ.:
New York, NY, 1999.
2. Hosomi, A.; Endo, M.; Sakurai, H. Chem. Lett. 1986, 365e368.
3. Hosomi, A. Acc. Chem. Res. 1988, 21, 200e206.
4. (a) Tubul, A.; Ouvrard, P.; Santelli, M. Synthesis 1991, 173e176; (b) Aouf, C.; El
Abed, D.; Giorgi, M.; Santelli, M. Tetrahedron 2009, 65, 5563e5570.
5. (a) Burtin, G.; Pellissier, H.; Santelli, M. Tetrahedron 1998, 54, 2075e2086; (b)
Burtin, G.; Pellissier, H.; Santelli, M. Tetrahedron 1998, 54, 4913e4922.
6. Ouvrard, P.; Tubul, A.; Santelli, M. Tetrahedron Lett. 1992, 33, 7519e7520.
7. Timberlake, C. F. J. Chem. Soc. 1957, 4987e4993.
8. Kimura, E.; Watanabe, A.; Kodama, M. J. Am. Chem. Soc. 1983, 105, 2063e2066.
9. Reddy, P. R.; Reddy, M. H. J. Chem. Soc., Dalton Trans. 1985, 239e242.
10. Novaroli, L.; Bouchard Doulakas, G.; Reist, M.; Rolando, B.; Fruttero, R.; Gasco,
A.; Carrupt -A, P. Helv. Chim. Acta 2006, 89, 144e152.
4.5.1. Spiro[4.4]non-2-ene (3). Yield 67%; 1H NMR (300 MHz,
CDCl3):
NMR (75 MHz, CDCl3):
(t). C9H14 (122.21): C 88.45, H 11.55; found C 88.55, H 11.68.
d
¼5.69 (br s, 2H), 2.29 (br s, 4H), 1.75e1.22 (m, 4H); 13C
d
¼129.9 (d), 45.9 (t), 45.1 (s), 40.5 (t), 24.1
4.5.2. 1,2-Bis-(1-methylcyclopent-3-enyl)ethane (9). Yield 85%; 1H
11. CRC Handbook of Chemistry and Physics, 90th ed.; Lide, D. R., Ed.; CRC: Boca-
Raton (FL), 2010.
NMR (300 MHz, CDCl3):
d
¼5.0 (m, 4H), 2.30e2.00 (m, 8H),
1.40e1.20 (m, 4H), 1.00 (s, 6H); 13C NMR (7 Hz, CDCl3):
d
¼129.4 (d)
12. (a) Flamini, A.; Cole-Hamilton, D. J.; Wilkinson, G. J. Chem. Soc., Dalton Trans.:
ꢀ
Inorg. Chem. 1978, 454e459; (b) Gomez-Carrera, A.; Mena, M.; Royo, P.; Ser-
(4C), 46.4 (t)(4C), 41.1 (s)(2C), 38.1 (t)(2C), 27.9 (q)(2C). C14H22
(190.17): C 88.35, H 11.65; found C 88.45, H 11.55.
rano, R. J. Organomet. Chem. 1986, 315, 329e335; (c) Funk, H.; Schlegel, A.;
Zimmermann, K. J. Prakt. Chem. 1956, 3, 320e332.
13. (a) Napolitano, E.; Fiaschi, R.; Mastrorilli, E. Synthesis 1986, 122e125; (b) Deb-
roy, P.; Shukla, R.; Lindeman, S. V.; Rathore, R. J. Org. Chem. 2007, 72, 1765e1769.
14. Saccomano, N. A.; Vinick, F. J.; Koe, B. K.; Nielsen, J. A.; Whalen, W. M.; Meltz, M.;
Phillips, D.; Thadieo, P. F.; Jung, S.; Chapin, D. S.; Lebel, L. A.; Russo, L. L.; Helweg, D.
A.; Johnson, J. L.; Ives, J. L.; Williams, I. H. J. Med. Chem. 1991, 34, 291e298.
15. (a) McKeown, N. B.; Helliwell, M.; Hassan, B. M.; Hayhurst, D.; Li, H.; Thompson,
N.; Teat, S. J. Chem.dEur. J. 2007, 228e234; (b) Li, T.-S.; Li, L.-J.; Lu, B.;
Yang, F. J. Chem. Soc., Perkin Trans. 1 1998, 3561e3564; (c) Butkus, E.; Berg, U.;
Stoncius, A.; Rimkus, A. J. Chem. Soc., Perkin Trans. 2 1998, 2547e2551; (d) Cole,
E. R.; Crank, G.; Minh, H. T. H. Aust. J. Chem. 1980, 33, 675e680.
4.5.3. 4-Methyl-4-(2-phenylethyl)cyclopentene (12a). Yield 85%; 1H
NMR (300 MHz, CDCl3): 7.38e7.18 (m, 5H), 5.72 (br s, H), 2.70e2.64
(m, 2H), 2.20e2.00 (4H), 1.83e1.77 (m, 2H), 1.21 (s, 3H); 13C NMR:
143.5 (s), 129.4 (d) (2C), 128.4 (d) (4C), 125.7 (d), 46.4 (t) (2C), 45.2
(t), 41.4 (s), 32.2 (t), 27.8 (q). C14H18 (186.29): C 90.26, H 9.74; found
C 89.98, H 9.68.
16. Galy, N.; Moraleda, D.; Santelli, M. Tetrahedron Lett. 2009, 50, 5238e5240.
17. (a) Tubul, A.; Santelli, M. Tetrahedron 1988, 44, 3975e3982; (b) Santelli, M.;
Tubul, A.; Morel-Fourrier, C. Selectivities in Lewis Acid Promoted Reactions
In. NATO ASI Series C; Schinzer, D., Ed.; Kluwer Academic: Dordrecht, 1989; Vol.
289, pp 127e145; (c) Pellissier, H.; Toupet, L.; Santelli, M. J. Org. Chem. 1994, 59,
1709e1713.
18. Titanium tetrachloride and nitromethane give a 1:1 complex with the nitro-
methane acts as a bidentate ligand, see: Norbury, A. H.; Sinha, A. I. P. J. Chem.
Soc. A 1966, 1814e1816.
19. Tubul, A.; Ouvrard, D.; Santelli, M. Bull. Soc. Chim. Fr. 1992, 129, 265e269.
20. (a) Pellissier, H.; Toupet, L.; Santelli, M. J. Org. Chem. 1998, 63, 2148e2153.
21. Marton, D.; Stivanello, D.; Tagliavini, G. J. Organomet. Chem. 1997, 540, 77e81.
22. (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446e452; (b)
Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18e29.
4.5.4. 4-Methyl-4-(2-anisylethyl)cyclopentene (12b). Yield 85%; 1H
NMR (300 MHz, CDCl3): 7.11 (d, J¼8.7 Hz, 2H), 6.83 (d, J¼8. Hz, 2H),
5.63 (br s, 2H), 3.78 (s, 3H), 2.56e2.50 (m, 2H), 2.31e2.08 (m, 4H),
1.71e1.65 (m, 2H), 1.12 (s, 3H); 13C NMR: 157.7 (s), 135.6 (s), 129.4
(d)(2C), 129.3 (d)(2C), 113.9 (d)(2C), 55.4 (q), 46.4 (t)(2C), 45.4 (t),
41.4 (s), 31.2 (t), 27.8 (q). C15H20O (216.32): C 83.28, H 9.32; found C
83.39, H 9.42.
4.5.5. 1,6-Diallyl-10-methylbicyclo[4.3.1]dec-3-ene (15). Yield 75%,
two isomers, 2:1; 1H NMR (500 MHz, CDCl3):
d
¼5.85e5.73 (m, 1H),
5.63e5.54 (m, 1H), 5.42e5.37 (½AB, d, J¼15.4, 6.0 Hz, 1H, minor
isomer), 5.37e5.32 (½AB, d, J¼15.2, 6.3 Hz, 1H, major isomer),
5.20e5.15 (½AB, d, J¼15.2, 8.7 Hz, 1H, major isomer), 2.34 (m, 1H),
2.31 (m, 1H), 2.25 (m, 1H), 2.21 (m, 1H), 2.11e2.03 (m, 4H), 1.70e1.1
(m, 7H), 0.78 (d, J¼7.0 Hz, 3H, minor isomer); 0.68 (d, J¼6.7 Hz, 3H,
23. Frischet al, M. J. Gaussian 03, Revision D.02; Gaussian: Pittsburgh, PA, 2003.
24. Nitromethane has a rather large Lewis acidity (
Lewis basicity (
a
¼0.22) and a relatively small
b
¼0.25), see: (a) Kamlet, M. J.; Abboud, J. M.; Abraham, H. M.;
Taft, R. W. J. Org. Chem. 1983, 48, 2877e2887; (b) Abraham, M. H.; Doherty, R.
M.; Kamlet, M. J.; Harris, J. M.; Taft, R. W. J. Chem. Soc., Perkin Trans. 2 1987,
913e920.

N. Galy et al. / Tetrahedron 67 (2011) 1448e1455
1455
25. The ionisation of triphenylmethyl chloride in nitromethane occurs extremely
readily, see: (a) Gelles, E.; Hughes, E. D.; Ingold, C. K. J. Chem. Soc. 1954,
2918e2929; (b) Evans, A. G.; Jones, J. A. G.; Osborne, G. O. Trans. Faraday Soc.
1954, 50, 16e23.
26. Boron cations are stabilized by dative interaction of one or two nitromethanes,
see: (a) Uddin, M. K.; Fujiyama, R.; Kiyooka, S.-i.; Fujio, M.; Tsuno, Y. Tetrahedron
Lett. 2004, 45, 3913e3916; (b) Kiyooka, S.-i.; Fujiyama, R.; Uddin, M. K.; Goh, K.;
Nagano, Y.; Fujio, M.; Tsuno, Y. Tetrahedron Lett. 2005, 46, 209e212.
27. H2C]NO(2ꢀ) group (aci-nitromethanato) is a bidentate ligand for ruthenium and
copper complexes with coordination through both oxygen atoms, see: (a) Cole-
Hamilton, D. J.; Wilkinson, G. Nouv. J. Chim. 1977, 1, 141e155; (b) Camus, A.;
Marsich, C. A.; Nardin, G.; Randaccio, L. Inorg. Chim. Acta 1976, 17, L33eL34.
28. Smirnov, V. O.; Ioffe, S. L.; Tishkov, A. A.; Khomutova, Y. A.; Nesterov, I. D.;
Antipin, M. Y.; Smit, W. A.; Tartakovsky, V. A. J. Org. Chem. 2004, 69, 8485e8488.
29. (a) Harder, S.; van Lenthe, J. H.; van Eikema Hommes, N. J. R.; Schleyer, P. v. R.
J. Am. Chem. Soc. 1994, 116, 2508e2514; (b) Gevorgyan, V.; Kˇ adota, I.; Yama-
ꢂ
moto, Y. Tetrahedron Lett. 1993, 34, 1313e1316; (c) Kocovsky, P. J. Org. Chem.
1988, 53, 5816e5819.
30. Sato, H.; Kusumi, T.; Imaye, K.; Kakisawa, H. Chem. Lett. 1975, 965e966.
31. (a) Olah, G. A.; DeMember, J. R.; Mo, Y. K.; Svoboda, J. J.; Schilling, P.; Olah, J. A.
J. Am. Chem. Soc. 1974, 96, 884e892; (b) Olah, G. A.; Fung, A. P.; Rawdah, T. N.
J. Org. Chem. 1980, 45, 4149e4153.
32. Pellissier, H.; Tubul, A.; Santelli, M. Tetrahedron Lett. 1993, 34, 827e830.
33. Galy, N.; Moraleda, D.; Santelli, M. in press.