A convenient way for the conversion of carboxylic esters into 2-substituted allyl halides

Article abstract of DOI:10.1055/s-2004-834869

The preparation of functionalized 2-substituted allyl bromides and chlorides from carboxylic esters is reported. The carboxylic esters were transformed first to 1-substituted cyclopropanols by treating with ethyl magnesium bromide in the presence of titan

Full text of DOI:10.1055/s-2004-834869

PRACTICAL SYNTHETIC PROCEDURES
1713
A Convenient Way for the Conversion of Carboxylic Esters into 2-Substituted
Allyl Halides
C
onversion of
C
ar
l
boxylic
e
E
sters into
g
2-Substituted Ally
G
l
Halides . Kulinkovich,* Yurii Y. Kozyrkov, Andrei V. Bekish, Evgenii A. Matiushenkov,
Ivan L. Lysenko
Department of Organic Chemistry, Belarusian State University, Skoriny av. 4, 220050 Minsk, Belarus
Fax +375(172)265609; E-mail: kulinkovich@bsu.by
Received 1 June 2004; revised 9 August 2004
PSP
No48
Abstract: The preparation of functionalized 2-substituted allyl bromides and chlorides from carboxylic esters is reported. The carboxylic
esters were transformed first to 1-substituted cyclopropanols by treating with ethylmagnesium bromide in the presence of titanium alkoxide.
Mesylation of the cyclopropanols followed by halide displacement of the sulfonate group to halogen, accompanied by cyclopropyl-allyl
rearrangement, affords the required allyl bromides and chlorides.
Key words: cyclopropanation, titanium alkoxides, cyclopropanols, cyclopropyl-allyl rearrangement, allyl halides
Scheme 1
Introduction
found that carboxylic esters are smoothly converted into
1-substituted cyclopropanols upon treatment with ethyl-
Transformation of the carbonyl group of carboxylic esters magnesium bromide in diethyl ether in the presence of
into other functionalities serves as the basis for various catalytic amounts of titanium(IV) isopropoxide.2 The
important methods of general preparative organic synthe- oxygen atom attached to a cyclopropane ring facilitates
sis. Most of these methods are based on intermolecular several regioselective ring-opening or ring expansion re-
carbon–carbon bond formation under the action of car- actions of substituted cyclopropanols.3 This allows the cy-
banionic reagents and are used mainly for the preparation clopropanation reaction to be used as an intermediate step
of alcohols, ketones, enol esters as well as some bifunc- in the conversion of an ester group into other functional-
tional compounds.1 For example, some years ago we have ities masked in a cyclopropanol fragment.
The present paper describes the full experimental proce-
dures for the transformation of carboxylic esters into 2-
substituted allyl halides bearing halogen, oxygen or nitro-
gen containing functional groups via the cationic cyclo-
SYNTHESIS 2005, No. 10, pp 1713–1717
Advanced online publication: 03.11.2004
DOI: 10.1055/s-2004-834869; Art ID: Z11204SS
© Georg Thieme Verlag Stuttgart · New York
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x.
x
x
.
2
0
0
4

1714
O. G. Kulinkovich et al.
PRACTICAL SYNTHETIC PROCEDURES
propyl-allyl isomerization of cyclopropyl sulfonates
(Scheme 1).4 Taking into account the fundamental impor-
tance of allyl halides as electrophilic synthetic intermedi-
ates and as precursors for allylic organometallic reagents,
the development of the efficient methods for the prepara-
tion of substituted allyl halides, contributes to further
progress in various concomitant fields of organic synthe-
sis.5
Scope and Limitations
It was supposed that cyclopropanation of carboxylic
esters with ethylmagnesium bromide in the presence of ti-
tanium(IV) isopropoxide is initiated by diisopropoxyti-
tanacyclopropane species formed by disproportionation
of the corresponding diethyltitanium precursors.2 They
act in situ as 1,2-dicarbanionic equivalents in the reactions
with esters leading to the corresponding cyclopropane de-
rivatives. This reaction can be realized in a catalytic ver-
sion.2c Carboxylic esters bearing halogen atoms, as well as
alkoxy, acetal, dialkylamine, trialkylsilyl and some other
insensitive to Grignard reagents groups usually smoothly
undergo cyclopropanation under the action of dialkoxyti-
tanacyclopropane reagents in diethyl ether.2d The cyclo-
propanation of the carboxylic esters having complex-
forming substituents in such conditions could be compli-
cated with precipitation of magnesium and titanium
alkoxides, leading to decrease in the cyclopropanol yields.
In some cases these difficulties can be overcome by the
use of solvents possessing better solvating properties,
such as tetrahydrofuran.6
Scheme 2
Scheme 3
Scheme 4
Recently, we have found convenient procedures for the
conversion of the sulfonates of the tertiary cyclopropanols
into 2-substituted allyl halides under the action of magne-
sium bromide, titanium tetrachloride, or some other metal
halides in diethyl ether.4 This reaction is induced by the
metal halide-assisted heterolytic cleavage of the carbon–
oxygen bond in cyclopropyl sulfonates which is accompa-
nied by a C-2–C-3 cyclopropane ring cleavage (cationic
cyclopropyl-allyl rearrangement).7 For example, 2-(bro-
momethyl)oct-1-ene was obtained in a 80% overall yield
starting from ethyl heptanoate using the cyclopropanation
of the latter with ethylmagnesium bromide in the presence
of titanium(IV) isopropoxide and treatment of tosylate of
1-hexylcyclopropanol with magnesium bromide
(Scheme 2).4
In summary, cyclopropanation of carboxylic esters with
ethylmagnesium bromide in the presence of titanium(IV)
isopropoxide, followed by transformation of obtained ter-
tiary cyclopropanols into the corresponding sulfonates
and treatment of the latter with metal halides, allows 2-
substituted allyl halides to be prepared in high overall
yields. The flexibility of this approach is demonstrated by
the syntheses of functionally substituted allyl halides,
which are not readily available by the preparation with use
of the conventional methods, such as allylic halogenation
of isopropenyl group,9 displacement of hydroxyl group in
the corresponding 2-substituted allyl alcohols,10 or cou-
pling of the Grignard reagents with 2-(bromomethyl)allyl
halides.11
Mesylate of (S)-1-tetrahydropyranyloxyethyl-1-cyclopro-
panol derived from ethyl (S)-lactate was successfully used
as a key intermediate in the synthesis of (2S,3R,7R/S)-3,7-
dimethyltridec-2-yl acetate and propionate, sex attractants
of pine sawfly Diprion pini (Scheme 3).5f
The alkaloids (S)-1-methylenopyrrolyzidine and (–)-he-
liotridane were synthesized starting from (S)-proline via a
mesylate of the corresponding cyclopropanol in a similar
way (Scheme 4).8
Synthesis 2005, No. 10, 1713–1717 © Thieme Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES Conversion of Carboxylic Esters into 2-Substituted Allyl Halides
1715
anhyd CH2Cl2 (200 mL), and cooled to 0 °C. MeSO2Cl (18.33 g,
160 mmol) was then added dropwise over 30 min to the stirred so-
lution. After 30 min, the reaction mixture was quenched with H2O
(200 mL). The organic layer was washed with H2O (100 mL), 10%
aq H2SO4 (100 mL), aq sat. NaHCO3 solution (100 mL), brine (100
mL), dried (MgSO4) and concentrated in vacuo. The methane-
sulfonate 4 (26.04 g, more than 90% purity on NMR data) was ob-
tained as a yellow oil and used in the next step without further
purification.
IR (CCl4): 3110, 1345, 1175, 1025, 660 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.76 (t, J = 7.0 Hz, 2 H), 2.98 (s,
3 H), 2.28 (t, J = 7.0 Hz, 2 H), 1.28–1.32 (m, 2 H), 0.79–0.83 (m, 2
We describe below three typical procedures which demonstrate the
different experimental techniques allowing to obtain a high prepar-
ative yields of the 2-substituted allyl halides bearing various func-
tional substituents (Scheme 1). In Procedure 1, we describe the
preparation of 4-chloro-2-(chloromethyl)but-1-ene (1) starting
from ethyl 3-chloropropanoate (2). 1-(2-Chloroethyl)cyclopropanol
(3)12 and mesylate 44 are obtained in high yields using the previous-
ly described standard experimental procedures. Mesylate 4 easily
reacts with magnesium bromide in ether at room temperature to af-
ford the corresponding allyl bromide in 70% isolated yield.4 How-
ever, the reaction with magnesium chloride or titanium(IV) chloride
in a similar conditions proceeds slowly and its completion requires
prolonged time (24 h or more). The interaction of mesylate 4 with
titanium(IV) chloride in dichloromethane leads to full consumption
of the substrate after 3 h to afford allyl chloride 1 in 73% yield. In
the next procedure (Procedure 2) THP-protected ethyl 3-hydroxy-
butyrate 5 is converted to 4-hydroxy-2-(bromomethyl)pent-1-ene
(6). The cyclopropanation of starting ester 5 under treatment with
ethylmagnesium bromide in the presence of catalytic amount of ti-
tanium(IV) isopropoxide in diethyl ether is accompanied with for-
mation of abundant precipitates. As a result, the cyclopropanol 7 is
formed at this reaction conditions in only 27% yield and near 32%
of starting compound 5 is recovered. The use of ether and tetrahy-
drofuran mixture as a solvent let to carry out the cyclopropanation
in homogenous conditions and to improve up to 88% the yield of the
cyclopropanol 7. The latter was converted without further purifica-
tion to the corresponding mesylate 8, which is not enough reactive
towards the action of magnesium bromide in diethyl ether, while
under reflux in a mixture of the ether and chloroform at reflux is
smoothly transformed to the corresponding allyl bromide 6 in 63%
overall yield after deprotection. In the last procedure (Procedure 3)
nitrogen containing allyl bromide 9 is prepared from cyclopropanol
10.13 Its mesylate does not react with magnesium bromide in diethyl
ether, probably due to good complexing properties of nitrogen at-
om, and leads to the formation of resinous products in chloroform.
This problem is solved by replacement of N-protecting benzhydryl
group with benzyloxycarbonyl (Cbz) group via N-deprotected cy-
clopropanol 11. Mesylation of carbamate 12 and subsequent treat-
ment of mesylate 13 with the solid magnesium bromide etherate in
refluxing chloroform resulted in 2-substituted allyl bromide 9 in
80% yield while the conversion of the mesylate 13 in Et2O or Et2O–
CHCl3 mixture was poor.
H).
13C NMR (100 MHz, CDCl3): d = 63.9, 40.6, 39.6, 39.1, 11.6.
4-Chloro-2-(chloromethyl)but-1-ene (1)14
A 500 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with 4 (18.30 g) and anhyd CH2Cl2 (200 mL).
TiCl4 (26.70 g, 140 mmol) was then added dropwise for a 20 min to
the stirred solution at r.t. After 3 h, the reaction mixture was
quenched with H2O (200 mL). The organic layer was washed with
H2O (2 × 100 mL), aq sat. NaHCO3 solution (50 mL), brine (100
mL), dried (CaCl2) and concentrated in vacuo. The crude product
was distilled in vacuo yielding allyl chloride 1 as a colorless liquid
(9.20 g, 63% from 2); bp 51–54 °C/11 mm Hg.
IR (CCl4): 1645, 675 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.26 (s, 1 H), 5.08 (s, 1 H), 4.07
(s, 2 H), 3.67 (t, J = 7.0 Hz, 2 H), 2.66 (t, J = 7.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 141.3, 117.2, 47.7, 42.1, 35.9.
Anal. Calcd for C5H8Cl2: C, 43.20; H, 5.80; Cl, 51.00. Found: C,
43.35; H, 5.66; Cl, 50.79.
1-[2-(Tetrahydro-2H-pyran-2-yloxy)propyl]cyclopropanol (7)
A 250 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with THP-protected ethyl 3-hydroxybutyrate (5;
5.00 g, 23.1 mmol), Ti(Oi-Pr)4 (1.64 g, 5.8 mmol) and anhyd THF
(40 mL) and cooled to 10 °C. The solution of EtMgBr prepared
from Mg turnings (1.70 g, 70 mmol) and EtBr (7.63 g, 70 mmol) in
a mixture of anhyd Et2O (30 mL), THF (30 mL) and benzene (3 mL)
was then added dropwise for a 4 h to the stirred solution. After 30
min, a solvent was removed under reduced pressure and the residue
was diluted with CH2Cl2 (100 mL). The obtained solution was
quenched with aq sat. NH4Cl solution (20 mL). The reaction mix-
ture was filtered and the inorganic precipitate was additionally
washed with CH2Cl2 (4 × 20 mL). The filtrate was washed with aq
sat. NaHCO3 solution (20 mL), dried (Na2SO4) and concentrated in
vacuo. The cyclopropanol 7 (4.49 g) was obtained as a pale yellow
oil and was used in the next step without further purification. A por-
tion of crude product (1.00 g) was purified by column chromatogra-
phy (cyclohexane–EtOAc, 20 g Merck silica gel) yielding
cyclopropanol 7 as a mixture of diastereomers (0.91 g, 88%).
1-(2-Chloroethyl)cyclopropanol (3)12
A 1000 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with ethyl 3-chloropropanoate (2; 20.49 g, 150
mmol), Ti(OPr-i)4 (4.33 g, 15 mmol) and anhyd Et2O (100 mL), and
cooled to 0 °C. A solution of EtMgBr prepared from Mg turnings
(9.00 g, 375 mmol) and EtBr (41.42 g, 380 mmol) in anhyd Et2O
(260 mL) was then added dropwise for a 1.5 h to the stirred solution.
After 30 min, the reaction mixture was quenched with 10% aq
H2SO4 (400 mL). The organic layer was washed with H2O (100
mL), aq sat. NaHCO3 solution (100 mL), brine (100 mL), dried
(Na2SO4) and concentrated in vacuo. The cyclopropanol 3 (16.80 g,
more than 90% purity on NMR data) was obtained as a pale yellow
oil and was used in the next step without further purification.
IR (CCl4): 3600, 3520, 3090 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.76–4.80 (m, 0.5 H), 4.64–4.67
(m, 0.5 H), 4.31 (br s, 1 H), 4.04–4.22 (m, 1 H), 3.88–3.97 (m, 1 H),
3.46–3.55 (m, 1 H), 1.66–1.90 (m, 3 H), 1.45–1.62 (m, 5 H), 1.31
(d, J = 6.1 Hz, 1.5 H), 1.16 (d, J = 6.2 Hz, 1.5 H), 0.62–0.81 (m, 2
H), 0.41–0.50 (m, 1 H), 0.32–0.40 (m, 1 H).
IR (CCl4): 3590, 3455 (br), 3080, 1135, 1010, 655 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.74 (t, J = 7.0 Hz, 2 H), 2.66 (s,
1 H), 1.99 (t, J = 7.0 Hz, 2 H), 0.75–0.79 (m, 2 H), 0.49–0.53 (m, 2
13C NMR (100 MHz, CDCl3): d = 99.4, 97.2, 75.2, 71.7, 63.8, 62.8,
54.5, 54.1, 44.6, 43.9, 31.2, 31.2, 25.3, 25.2, 22.0, 20.5, 19.9, 19.8,
14.3, 13.7, 12.0, 11.9.
H).
13C NMR (100 MHz, CDCl3): d = 53.9, 41.9, 41.0, 13.3.
1-(2-Chloroethyl)cyclopropyl Methanesulfonate (4)4
A 500 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with 3 (16.80 g), Et3N (20.24 g, 200 mmol) and
Anal. Calcd for C11H20O3: C, 65.97; H, 10.07; O, 23.97. Found: C,
66.14; H, 10.23; O, 23.63.
Synthesis 2005, No. 10, 1713–1717 © Thieme Stuttgart · New York

1716
O. G. Kulinkovich et al.
PRACTICAL SYNTHETIC PROCEDURES
1-[2-(Tetrahydro-2H-pyran-2-yloxy)propyl]cyclopropyl Meth-
anesulfonate (8)
cooled to –10 °C. The colorless crystals formed were filtered and
washed with the same solvent (2 mL) giving cyclopropanol 11 (2.68
g, 95%); mp 81–82 °C (Et2O).
IR (CHCl3): 3420 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.4 (br s, 2 H), 3.35–3.50 (m, 1 H),
2.97 (td, J = 11.5, 3.0 Hz, 1 H), 2.32 (dd, J = 10.0, 4.0 Hz, 1 H),
2.13–2.26 (m, 1 H), 1.55–2.1 (m, 5 H), 0.95–1.20 (m, 2 H), 0.72–
0.90 (m, 2 H).
A 250 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with cyclopropanol 7 (4.49 g), Et3N (6.98 g, 69
mmol) and Et2O (100 mL) and cooled to 0 °C. MeSO2Cl (4.00 g, 35
mmol) was then added dropwise over 30 min to the stirred solution.
After 30 min, the reaction mixture was quenched with H2O (100
mL) and extracted with Et2O (2 × 20 mL). The combined organic
fractions were dried (Na2SO4) and concentrated in vacuo. The meth-
anesulfonate 8 (6.18 g) was obtained as a yellow liquid and used in
the next step without further purification. A portion of crude prod-
uct (1.00 g) was purified by column chromatography (cyclohexane–
EtOAc, 20 g Merck silica gel) affording methanesulfonate 8 as a
mixture of diastereomers (0.91 g, 87% from ester 5).
13C NMR (100 MHz, CDCl3): d = 64.0, 56.9, 47.0, 27.8, 25.6, 24.5,
12.6, 11.2.
Anal. Calcd for C8H15NO: C, 68.04; H, 10.71. Found: C, 68.15; H,
10.69.
IR (CCl4): 3090 cm–1.
Benzyl 2-(1-Hydroxycyclopropyl)piperidine-1-carboxylate (12)
A 100 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with 11 (1.41 g, 10 mmol), benzyl chloroformate
(2.05 g, 12 mmol) and CH2Cl2 (20 mL) and cooled to –10 °C. A
50% aq solution of NaOH (4 mL) was added dropwise to the stirred
mixture. The reaction mixture was then stirred at r.t. for 6 h, the or-
ganic layer was separated, dried (Na2SO4) and concentrated in vac-
uo. The crude product was purified by column chromatography
(benzene, then benzene–Et2O, 1:1, 30 g Merck silica gel) yielding
12 as a pale yellow oil (2.45 g, 89%).
1H NMR (400 MHz, CDCl3): d = 4.75–4.79 (m, 0.5 H), 4.69–4.73
(m, 0.5 H), 4.06–4.22 (m, 1 H), 3.85–3.95 (m, 1 H), 3.44–3.53 (m,
1 H), 2.99 (s, 1.5 H), 2.98 (s, 1.5 H), 1.99–2.08 (m, 1 H), 1.65–1.92
(m, 3 H), 1.45–1.60 (m, 4 H), 1.15–1.32 (m, 2 H), 1.30 (d, J = 6.6
Hz, 1.5 H), 1.20 (d, J = 6.1 Hz, 1.5 H), 0.66–0.89 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 99.2, 94.9, 71.5, 67.9, 64.3, 64.2,
62.7, 61.9, 43.2, 43.0, 39.8, 31.1, 30.9, 25.5, 25.4, 22.3, 19.9, 19.3,
19.2, 12.1, 11.9, 11.6, 11.4.
IR (CCl4): 3605, 3405, 3060, 3000, 2920, 1685, 1420, 1320, 1160,
1025, 695 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.24–7.42 (m, 5 H), 5.16 (s, 2 H),
3.9 (br s, 1 H), 3.42–3.75 (m, 2 H), 3.2–3.35 (m, 1 H), 1.70–2.00 (m,
3 H), 1.42–1.64 (m, 3 H), 0.70–0.84 (m, 3 H), 0.48–0.60 (m, 1 H).
4-(Bromomethyl)pent-4-en-2-ol (6)
A 500 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with methanesulfonate 8 (6.18 g) and anhyd
CHCl3 (120 mL). A solution of MgBr2 prepared from Mg turnings
(1.41 g, 58 mmol) and 1,2-dibromoethane (11.46 g, 61 mmol) in
Et2O (60 mL), was then added in one portion to the stirred solution
at r.t. The reaction mixture was refluxed under argon for 1.5 h, then
cooled to r.t., quenched with H2O (100 mL) and extracted with Et2O
(4 × 20 mL). The combined organic fractions were dried (Na2SO4)
and concentrated in vacuo. The residue was diluted with MeOH (40
mL). Pyridinium p-toluenesulfonate (PPTS, 0.10 g) was then added
to the solution and the mixture was refluxed under argon for 10 min
and then concentrated in vacuo. The residue was diluted with
CH2Cl2 (50 mL), washed with aq sat. NaHCO3 solution (20 mL),
and the aqueous layer was back-extracted with CH2Cl2 (4 × 5 mL).
The combined organic fractions were dried (Na2SO4) and concen-
trated in vacuo. The crude product was purified by column chroma-
tography (cyclohexane–EtOAc, 15:1, 60 g Merck silica gel)
yielding allyl bromide 6 as a pale yellow oil (2.61 g, 63% from 5).
Anal. Calcd for C16H21NO3: C, 69.79; H, 7.69. Found: C, 69.96; H,
7.55.
Benzyl 2-[1-(Bromomethyl)vinyl]piperidine-1-carboxylate (9)
A 100 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with cyclopropanol 12 (2.20 g, 8 mmol), Et3N
(2.43 g, 24 mmol) and Et2O (30 mL) and cooled to –10 °C.
MeSO2Cl (1.37 g, 12 mmol) was then added dropwise for a 10 min
to the stirred solution. After stirring for 2 h at r.t., the reaction mix-
ture was quenched with H2O (10 mL). The organic layer was
washed with aq 2 N HCl solution (5 mL), aq sat. NaHCO3 solution
(5 mL), then dried (Na2SO4) and concentrated in vacuo yielding me-
sylate 13 as a colorless oil (2.82 g). The latter was diluted with
CHCl3 (16 mL) and added to MgBr2·OEt2 prepared from Mg turn-
ings (0.58 g, 24 mmol) and 1,2-dibromoethane (4.51 g, 24 mmol) in
Et2O (30 mL) followed by removal of Et2O in vacuo. The stirred re-
action mixture was refluxed for 1.5 h, then cooled to 0 °C and
quenched with H2O (15 mL). The organic fraction was dried
(Na2SO4) and concentrated in vacuo. The crude product was puri-
fied by column chromatography (cyclohexane, then benzene–Et2O,
1:1, 25 g Merck silica gel) yielding 9 as a pale yellow oil (2.16 g,
80%).
IR (CCl4): 3610, 3480, 3080, 1630 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.30 (br s, 1 H), 5.07–5.08 (m, 1
H), 3.98–4.07 (m, 3 H), 2.45 (ddd, J = 14.5, 4.0, 1.1 Hz, 1 H), 2.27
(ddd, J = 14.5, 8.8, 0.8 Hz, 1 H), 1.60 (br s, 1 H), 1.25 (d, J = 6.2
Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 142.6, 117.9, 65.7, 43.4, 36.5,
23.2.
Anal. Calcd for C6H11BrO: C, 40.25; H, 6.19. Found: C, 40.38; H,
6.08.
IR (CCl4): 2935, 1690, 1420, 1255, 1170, 700 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.27–7.39 (m, 5 H), 5.46 (d,
J = 1.5 Hz, 1 H), 5.16 (s, 2 H), 5.08–5.15 (m, 2 H), 4.03–4.12 (m, 1
H), 3.90–3.98 (m, 2 H), 2.75–2.85 (m, 1 H), 2.0–2.08 (m, 1 H),
1.57–1.77 (m, 3 H), 1.40–1.56 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 155.8, 142.7, 136.8, 128.4, 127.9,
127.8, 117.8, 67.2, 52.6, 40.6, 33.9, 26.2, 25.4, 19.7.
1-(Piperidin-2-yl)cyclopropanol (11)
A 100 mL round-bottom flask, equipped with a magnetic stirring
bar, was charged with 1-(1-benzhydrylpiperidin-2-yl)cyclo-
propanol13 (10; 6.15 g, 20 mmol), 20% Pd(OH)2 on charcoal (0.50
g) and MeOH (50 mL). The reaction mixture was stirred until the
calculated amount of H2 gas was absorbed. The catalyst was re-
moved by filtration and the filtrate was concentrated in vacuo. The
residue was diluted with hexane–Et2O mixture (1:1, 10 mL) and
Anal. Calcd for C16H20BrNO2: C, 56.82; H, 5.96. Found: C, 57.14;
H, 5.69.
Synthesis 2005, No. 10, 1713–1717 © Thieme Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES Conversion of Carboxylic Esters into 2-Substituted Allyl Halides
1717
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