Stereoselective synthesis of (7aS)-1-methylenehexahydro-1H-pyrrolizine and (-)-heliotridane from N-diphenylmethyl-(S)-proline ethyl ester

Article abstract of DOI:10.1007/s11178-005-0123-0

Alkaloid (7aS)-1-methylenehexahydro-1H-pyrrolizine was synthesized from N-diphenylmethyl-(S)-proline ethyl ester by cyclopropanation of the ester group with ethylmagnesium bromide in the presence of titanium tetraisopropoxide, replacement of the protectin

Full text of DOI:10.1007/s11178-005-0123-0

Russian Journal of Organic Chemistry, Vol. 41, No. 1, 2005, pp. 70 -74. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005,
pp. 73-77.
Original Russian Text Copyright Ó 2005 by Lysenko, Kulinkovich.
Stereoselective Synthesis of (7aS)-1-Methylenehexahydro-
1H-pyrrolizine and (–)-Heliotridane from N-Diphenylmethyl-
(S)-proline Ethyl Ester
I. L. Lysenko and O. G. Kulinkovich
Belarussian State University, pr. Skoriny 4, Minsk, 220050 Belarus
Received November 20, 2003
Abstract—Alkaloid (7aS)-1-methylenehexahydro-1H-pyrrolizine was synthesized from N-diphenylmethyl-(S)-
proline ethyl ester by cyclopropanation of the ester group with ethylmagnesium bromide in the presence of
titanium tetraisopropoxide, replacement of the protecting group on the nitrogen atom, and cationic cyclopropyl–
allyl isomerization of (S)-1-(1-ethoxycarbonylpyrrolidin-2-yl)cyclopropyl sulfonate into the corresponding allyl
bromide. Stereoselective reduction of (7aS)-1-methylenehexahydro-1H-pyrrolizine with sodium tetrahydridoborate
in the presence of nickel chloride afforded (–)-heliotridane [(1S,7aS)-1-methylhexahydro-1H-pyrrolizine] in high
yield.
Substituted cyclopropanols have found increasing
application as intermediate products in organic synthesis
due mainly to the development of convenient procedures
for their preparation and transformation into com-
pounds belonging to other classes via opening of the
three-membered ring [1, 2]. We recently found [3, 4]
that N-benzyl-a-amino acid esters smoothly react with
ethylmagnesium bromide in the presence of titanium
tetraisopropoxide to give the corresponding 1-amino-
alkylcyclopropanols [5]. Thus, isomerization of the
cyclopropanation product obtained from N-diphenyl-
methylpipecolic acid ethyl ester gave the corresponding
ethyl ketone, and the subsequent stereoselective reduction
of the carbonyl group therein afforded (±)-a- and (±)-b-
conhydrins [4]. The present article describes an effective
procedure for the synthesis of (7aS)-1-methylene-
hexahydro-1H-pyrrolizine (I) which is the major alkaloid
isolable from Crotalaria Anagiroides [6] and Crotalaria
Damarensis [7], as well as of a necine base, (–)-helio-
tridane (II) [8], which is based on cationic cyclopropyl–
allyl isomerization of the cyclopropanation product of
N-diphenylmethyl-(S)-proline ethyl ester (III). The
synthesis of racemic 1-methylenehexahydro-1H-pyr-
rolizine was reported previously [9]; however, an attempt
to isolate particular enantiomers through the correspond-
ing tartrates gave compound I with a poor optical purity.
N-Diphenylmethyl-(S)-proline ethyl ester (III) was
treated with 3 equiv of ethylmagnesium bromide in the
presence of 0.2 equiv of titanium tetraisopropoxide at
room temperature to obtain 92% of cyclopropanol IV.
Scheme 1.
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2+
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(W 1ꢆꢃ'0)
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III, IV, R = Ph2CH; V, R = H; VIII, R' = EtOC(O); IX, R' = H.
1070-4280/05/4101-0070Ó2005 Pleiades Publishing, Inc.

STEREOSELECTIVE SYNTHESIS OF (7aS)-1-METHYLENEHEXAHYDRO-1H-PYRROLIZINE
71
Removal of the protecting diphenylmethyl group from
compound IV by hydrogenation over palladium catalyst
[4, 10] and the subsequent acylation of pyrrolidine V with
ethyl chloroformate gave substituted cyclopropanol VI
in a good yield (Scheme 1). The latter was converted
into the corresponding methanesulfonate which was
subjected to cyclopropyl–allyl rearrangement to allyl
bromide VII by the action of magnesium bromide in
diethyl ether according to the procedure reported in [11].
However, the isomeriza-tion under heterogeneous
conditions afforded compound VII in a poor yield. Better
results were obtained when the reaction was carried out
with magnesium bromide–ether complex (MgBr2 · Et2O)
in boiling chloroform. In this case, the reaction mixture
was homogeneous, and allyl bromide VII was obtained
in 88% yield. Compound VII was then converted into
the corresponding organozinc derivative which was
brought into condensation with paraformaldehyde,
followed by removal of the protecting group from the
nitrogen atom in VIII. We thus isolated homoallyl alcohol
IX in a moderate yield. Intramolecular cyclization of
compound IX was smoothly effected by the action of
triphenylphosphine and carbon tetrachloride in the
presence of triethylamine. As a result, (7aS)-1-
methylenehexahydro-1H-pyrrolizine (I) was formed;
taking into account high volatility of I, the product was
isolated from the reaction mixture as the corresponding
picrate [12].
To conclude, it should be noted that the proposed
procedure for efficient transformation of the carboxylic
functionality in (S)-proline to allyl bromide moiety opens
a simple synthetic route to compound VII which can be
regarded as a promising chiral building block. In the present
work it was successfully used to synthesize pyrrolizidine
alkaloids I and II.
EXPERIMENTAL
The 1H NMR spectra of solutions of compounds I–X
in chloroform-d were obtained on a Bruker AC 400
instrument (400 MHz). The IR spectra were recorded
from solutions in carbon tetrachloride using a Specord
75 IR spectrometer. Diethyl ether and benzene were dried
and distilled over metallic sodium; tetrahydrofuran was
distilled over lithium tetrahydridoaluminate; paraform-
aldehyde was dried under reduced pressure over
phosphorus(V) oxide.
(7aS)-1-Methylenehexahydro-1H-pyrrolizine (I).
A mixture of 0.58 g (4.1 mmol) of compound IX, 2.15 g
(8.2 mmol) of triphenylphosphine, 0.8 ml (8.3 mmol) of
carbon tetrachloride, and 1.14 ml (8.2 mmol) of
triethylamine in 9 ml of dimethylformamide was stirred
for 48 h at room temperature, 4 ml of 2 M hydrochloric
acod was added, and the solvent was distilled off on stirring
under reduced pressure at a temperature not exceeding
60°C (oil bath). Water, 5 ml, was added to the residue,
and the mixture was extracted with methylene chloride
(3 ´ 5 ml). Potassium hydroxide, 2 g, was added to the
aqueous phase, and the product was extracted into diethyl
ether (3 ´ 5 ml). The extract was dried over solid
potassium hydroxide, the solvent was distilled off under
atmospheric pressure, and a solution of 1.0 g (4.3 mmol)
of picric acid in 4 ml of a 1 : 1 mixture of ethanol with
diethyl ether was added to the residue. The precipitate
was filtered off, washed with 1 ml of a cold ethanol–
diethyl ether mixture (1 : 1), and dried under reduced
pressure. We thus isolated 1.15 g (80%) of compound I
picrate as fine yellow crystals with mp 217.5–218.5°C
(from ethanol); published data [7]: mp 218–219°C.
1H NMR spectrum (CDCl3, TMS), d, ppm: 1.96–2.16 m
(2H), 2.20–2.30 m (1H), 2.43–2.53 m (1H), 2.75–2.85 m
(1H), 2.89–3.00 m (1H), 3.04–3.14 m (2H), 3.76–3.86 m
(1H), 3.87–3.97 m (1H), 3.71–3.79 m (1H), 5.13 d
(1H, J = 2.3 Hz), 5.26 d (1H, J = 2.1 Hz), 8.87 s (2H),
11.82 br.s (1H). 13C NMR spectrum (CDCl3), dC, ppm:
25.05, 31.09, 31.68, 53.40, 55.23, 69.49, 110.29, 126.55,
128.36, 141.63, 144.60, 162.18. (7aS)-1-Methylene-
hexahydro-1H-pyrrolizine (I) was isolated from the
Culvenor and Smith previously reported [6, 7] that
hydrogenation of methylenepyrrolizine I over theAdams
catalyst or Raney nickel gives a mixture of heliotridane
(II) and its diastereoisomer X, the latter slightly prevailing.
We succeeded in effecting a similar transformation with
a considerably higher stereoselectivity using the system
sodium tetrahydridoborate–nickel(II) chloride in methanol
[13] as reducing agent. In this case, the ratio of (–)-helio-
tridane (II) and (–)-pseudoheliotridane (X) was 11 : 1
(Scheme 2); it was determined from the intensity ratio of
the methyl proton signals in the 1H NMR spectrum of
a mixture of the corresponding picrates [14, 15]. Pure
(–)-heliotridane picrate was isolated by recrystallization.
Scheme 2.
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RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

72
LYSENKO, KULINKOVICH
1
picrate by treatment with aqueous alkali. H NMR
spectrum (CDCl3, TMS), d, ppm: 1.53–1.63 m (1H), 1.7–
1.85 m (2H), 2.02–2.12 m (1H), 2.45–2.70 m (4H), 2.95–
3.1 m (2H), 3.8–3.3.86 m (1H), 4.82 s (1H), 4.94 s (1H).
13C NMR spectrum (CDCl3), dC, ppm: 25.60, 32.32,
32.68, 52.76, 54.28, 67.61, 104.56, 154.71.
(1H), 2.92–3.08 m (1H), 3.4–3.54 m (1H), 3.92 q (2H,
J = 7 Hz), 4.80 s (1H), 7.08–7.34 m (6H), 7.36–7.56 m
(4H). Found, %: C 77.59; H 7.37. C20H23NO2.
Calculated, %: C 77.71; H 7.45.
1-[(2S)-1-Diphenylmethylpyrrolidin-2-yl]cyclo-
propanol (IV). A 1 M solution of ethylmagnesium
bromide in diethyl ether, 15 ml (15 mmol), was added
over a period of 40–60 min under stirring at room
temperature to a solution of 1.51 g (5 mmol) of ester III
and 0.28 ml (1 mmol) of titanium tetraisopropoxide in
15 ml of diethyl ether. The mixture was left overnight,
cooled to 0°C, treated with 12 ml of 2 M hydrochloric
acid, and stirred for 2–4 h at room temperature. The
organic phase was separated, the oily material was
dissolved in 10 ml of methylene chloride, and the aqueous
phase was additionally treated with methylene chloride
(2 ´ 10 ml). The extracts were combined, washed in
succession with saturated aqueous solutions of sodium
chloride (5 ml) and sodium hydrogen carbonate (5 ml),
and dried over anhydrous sodium sulfate. The solvent
was distilled off under reduced pressure to obtain 1.35 g
(92%) of compound IV with [a]D20 = –22.4° (c = 10,
(–)-Heliotridane (II). Powdered sodium tetra-
hydridoborate, 10 mg (0.26 mmol), was added in portions
under stirring to a solution of 10 mg (0.08 mmol) of
compound I and 20 mg (0.08 mmol) of nickel(II) chloride
hexahydrate in 0.4 ml of methanol. The mixture was stir-
red for 10 min, 1 ml of diethyl ether was added, and
the precipitate was filtered off. Picric acid, 20 mg
(0.08 mmol), was added to the filtrate, the solvent was
removed under reduced pressure, and 1H NMR spectrum
of the dry residue was recorded. The intensity ratio of
the methyl proton signals at d 1.14 {(–)-heliotridane
picrate; cf. [14]} and 1.20 ppm {(–)-pseudoheliotridane
picrate; cf. [15]} was 11 : 1. The resulting mixture of II
and X was recrystallized from 0.5 ml of ethanol to isolate
25 mg (81%) of (–)-heliotridane II picrate with mp 245–
246°C (from ethanol); published data [16]: mp 245.5–
1
–1 1
246°C. H NMR spectrum (CDCl3, TMS), d, ppm:
Et2O). IR spectrum: n OH 3455 cm . H NMR spectrum
1.14 d (3H, J = 6.5 Hz), 1.68–1.82 m (2H), 2.04–2.24 m
(4H), 2.63 oct (1H, J = 6.5 Hz), 2.74–2.86 m (1H),
3.12 d.d (1H, J1 = 12, J2 = 7 Hz), 3.68 sept (1H, J =
6.2 Hz), 4.0–4.1 m (1H), 4.24–4.34 m (1H), 8.89 s (2H),
11.42 br.s (1H) (cf. [14]).
(CDCl3, TMS), d, ppm: 0.04 d.d.d (1H, J1 = 11, J2 = 6,
J3 = 5 Hz), 0.24 d.d.d (1H, J1 = 11, J2 = 6, J3 = 5 Hz),
0.54 d.d.d (1H, J1 = 11, J2 = 6, J3 = 5 Hz), 0.74 d.d.d (1H,
J1 = 11, J2 = 6, J3 = 5 Hz), 1.5–2.10 m (5H), 2.40–2.56 m
(2H), 3.02–3.18 m (1H), 5.14 s (1H), 7.12–7.44 s (10H).
Found, %: C 81.98; H 7.81. C20H23NO. Calculated, %:
C 81.91; H 7.92.
(–)-Heliotridane (II) was isolated from the picrate
1
by the action of aqueous alkali. H NMR spectrum
(CDCl3, TMS), d, ppm: 0.98 d (3H, J = 7 Hz), 1.28–
1.44 m (2H), 1.52–1.76 m (3H), 1.77–1.88 m (1H),
2.24 d.sext (1H, J1 = 10, J2 = 7 Hz), 2.44 t.d (1H, J1 = 10,
J2 = 6 Hz), 2.54 d.d.d (1H, J1 = 11, J2 = 7.5, J3 = 3.5 Hz),
2.96 d.d.d (1H, J1 = 11, J2 = 9, J3 = 6 Hz), 3.14 d.d.d (1H,
J1 = 10, J2 = 7, J3 = 3 Hz), 3.39 d.t (1H, J1 = 9.5, J2 =
7 Hz). 13C NMR spectrum (CDCl3), dC, ppm: 15.11,
26.53, 26.68, 32.07, 35.64, 54.42, 56.48, 68.32.
1-[(2S)-Pyrrolidin-2-yl]cyclopropanol (V). A solu-
tion of 5.86 g (20 mmol) of compound IV in 50 ml of
methanol containing 0.50 g of 20% Pd(OH)2/C was stirred
under a hydrogen pressure of 1 atm until hydrogen was
no longer absorbed (500 ml, 22 mmol). The catalyst was
filtered off, the filtrate was evaporated under reduced
pressure, 10 ml of hexane was added to the residue, the
mixture was cooled to –10°C, and the precipitate was
filtered off, washed on a filter with a small amount of
cold diethyl ether, and dried under reduced pressure. Yield
N-Diphenylmethyl-(S)-proline ethyl ester (III).
A mixture of 16.1 g (112.5 mmol) of (S)-proline ethyl
ester, 27.66 g (112 mmol) diphenylmethyl bromide, 11 g
(130 mmol) of sodium hydrogen carbonate, and 40 ml of
toluene was heated for 4 h under reflux with simultaneous
removal of water, the precipitate of inorganic salts was
filtered off, and the solvent was removed under reduced
pressure. The residue was distilled in a vacuum to isolate
31.67 g (91%) of compound III, bp 166–169°C (1–2 mm),
[a]D17 = –79° (c = 10, Et2O). IR spectrum: n C=O
2.16 g (85%), colorless leaflets, mp 48–50°C, [a]D16
=
1
–19.5° (c = 4, MeOH ). H NMR spectrum (CDCl3,
TMS), d, ppm: 0.40–0.56 m (2H), 0.70–0.82 m (2H),
1.62–1.96 m (4H), 2.80–3.14 m (3H), 4.30 br.s (2H).
13C NMR spectrum (CDCl3), dC, ppm: 10.78, 12.97,
25.45, 27.11, 46.26, 54.82, 65.25. Found, %: C 66.11;
H 10.30. C7H13NO. Calculated, %: C 66.07; H 10.33.
Ethyl (2S)-2-(1-hydroxycyclopropyl)-1-pyr-
rolidinecarboxylate (VI). Ethyl chloroformate, 1.61 ml
(16.5 mmol), was added dropwise to a solution of 2.0 g
–1
1720 cm . 1H NMR spectrum (CDCl3, TMS), d, ppm:
1.10 t (3H, J = 7 Hz), 1.76–2.26 m (4H), 2.56–2.74 m
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

STEREOSELECTIVE SYNTHESIS OF (7aS)-1-METHYLENEHEXAHYDRO-1H-PYRROLIZINE
73
(15.7 mmol) of compound V and 2.4 ml (17.3 mmol) of
triethylamine in 40 ml of methylene chloride, cooled to
–20°C. The mixture was stirred for 1 h at room tempera-
ture, 10 ml of 1 M hydrochloric acid was added, and the
organic phase was separated, washed with 10 ml of a
saturated solution of sodium hydrogen carbonate, and
dried over sodium sulfate. The drying agent was
separated, the solvent was removed under reduced
pressure, and the residue was subjected to
chromatography on silica gel using first benzene and then
benzene–diethyl ether (1 : 1) as eluent. Yield 2.83 g
(90%). [a]D16 = –53° (c = 10, Et2O ). IR spectrum, n,
(3H), 2.08–2.20 m (1H), 3.44–3.60 m (2H), 3.90–4.20 m
(4H), 4.48–4.56 m (1H), 4.98–5.12 m (1H), 5.20–5.32
m (1H). 13C NMR spectrum (CDCl3), dC, ppm: 14.66,
31.90, 33.46, 46.73, 59.10, 61.00, 64.90, 114.70, 146.20,
158.67. Found, %: C 45.82; H 6.15. C10H16BrNO2.
Calculated, %: C 45.65; H 6.32.
Ethyl (2S)-2-[1-(2-hydroxyethyl)vinyl]-1-pyr-
rolidinecarboxylate (VIII).Amixture of 1.31 g (5 mmol)
of compound VII, 0.98 g (15 mmol) of zinc powder,
0.45 g (15 mmol) of paraformaldehyde, and 0.22 ml
(2.5 mmol) of 1,2-dibromoethane in 5 ml of tetra-
hydrofuran was heated for 2 h under reflux with stirring
in an argon atmosphere. The mixture was evaporated
under reduced pressure, the residue was treated with
5 ml of 1 M hydrochloric acid on stirring, 10 ml of diethyl
ether was addded, and the precipitate was filtered off
and washed on a filter with 5 ml of diethyl ether. The
organic phase was separated from the filtrate, washed
with 3 ml of a saturated solution of sodium hydrogen
carbonate, and dried over sodium sulfate. By flash
chromatography on silica gel using first benzene–diethyl
ether (5 : 1) and then diethyl ether as eluent we isolated
0.65 g (61%) of compound VIII as a colorless oily
substance. [a]D17 = –14° (c = 5, Et2O). IR spectrum, n,
–1
cm : 3573 (O–H), 3387 (O–H), 1653 (C=O). 1H NMR
spectrum (CDCl3, TMS), d, ppm: 0.33–0.41 m (1H), 0.58–
0.67 m (1H), 0.68–0.76 m (2H), 1.20 t (3H, J = 7 Hz),
1.60–1.78 m (1H), 1.8–2.2 m (3H), 3.2–3.58 m (3H),
3.8–3.72 m (1H), 4.0–4.12 m (2H). Found, %: C 60.38;
H 8.52. C10H17NO3. Calculated, %: C 60.25; H 8.65.
Ethyl (2S)-2-(1-bromomethylvinyl)-1-pyrrolidine-
carboxylate (VII). A solution of 3.48 g (17.5 mmol) of
compound VI and 7.3 ml (52.5 mmol) of triethylamine in
30 ml of diethyl ether was cooled to –10°C, and 2.0 ml
(26.3 mmol) of methanesulfonyl chloride was added
dropwise. When the addition was complete, the cooling
bath was removed, the mixture was stirred for 2 h at
room temperature, and 20 ml of water was added. The
organic phase was separated, washed with 10 ml of 2 M
hydrochloric acid and 10 ml of a saturated solution of
sodium hydrogen carbonate, and dried over sodium sulfate.
Removal of the solvent under reduced pressure gave
4.81 g (99%) of crude ethyl (2S)-2-(1-methylsulfonyl-
oxycyclopropyl)-1-pyrrolidinecarboxylate. The product
was dissolved in 20 ml of chloroform, and solid magnesium
bromide–ether complex [prepared from 1.26 g (52 mmol)
of magnesium and 4.5 ml (52 mmol) of 1,2-dibromoethane
in 20 ml of diethyl ether, followed by vacuum distillation
of the solvent] was added. The mixture was heated for
1 h under reflux with stirring (oil bath, 80°C), cooled to
0°C, and treated with 10 ml of water on stirring. The
organic phase was separated, the aqueous phase was
extracted with 5 ml of chloroform, and the combined
extracts were washed in succession with 5 ml of 1 M
hydrochloric acid and 5 ml of a saturated solution of
sodium hydrogen carbonate, dried over sodium sulfate,
and evaporated. The residue was subjected to flash
chromatography on silica gel using benzene–diethyl ether
(first 10 : 1 and then 1 : 1) as eluent. Yield 4.08 g (89%),
yellowish oily substance, [a]D16 = –13° (c = 10, Et2O). IR
–1
1
cm : 3400 (O–H), 1665 (C=O). H NMR spectrum
(CDCl3, TMS), d, ppm: 1.15–1.25 m (3H), 1.6–1.75 m
(1H), 1.75–2.10 m (3H), 1.15–1.25 m (1H), 2.27–2.30 m
(1H), 3.37–3.55 m (3H), 3.67–3.90 m (2H), 4.05–4.15 m
(2H), 4.20–4.30 m (1H), 4.85–4.95 m (2H). 13C NMR
spectrum (CDCl3), dC, ppm: 14.65, 23.26, 31.16, 37.25,
46.87, 60.51, 61.04, 110.33, 155.06. Found, %: C 61.95;
H 8.98. C11H19NO3. Calculated, %: C 62.11; H 8.83.
3-[(2S)-Pyrrolidin-2-yl)-3-buten-1-ol (IX). A mix-
ture of 1.58 g (7.4 mmol) of compound VIII, 1.8 g of
potassium hydroxide, and 5 ml of a 80% aqueous solution
of ethylene glycol was heated for 3 h at the boiling point
with stirring. The product was extracted into diethyl ether
(3 ´ 5 ml), and the combined extracts were dried over
sodium sulfate, filtered through a layer of activated
aluminum oxide, and evaporated under reduced pressure.
Yield 0.89 g (85%), colorless oily substance. [a]D13
=
–1
–86° (c = 5, Et2O). IR spectrum, n, cm : 3347 (O–H,
N–H), 1680 (C=C). 1H NMR spectrum (CDCl3, TMS),
d, ppm: 1.65–1.94 m (4H), 2.32 t (2H, J = 4.6 Hz), 2.94–
3.04 m (2H), 3.44–3.53 m (1H), 3.66–3.75 m (2H), 4.36–
4.56 br.s (2H), 4.87 m (1H), 4.94 m (1H). 13C NMR
spectrum (CDCl3), dC, ppm: 25.57, 30.08, 36.48, 46.16,
63.04, 63.14, 114.17, 150.30. Found, %: C 68.04; H 10.71.
C8H15NO. Calculated, %: C 67.92; H 10.85.
–1
1
spectrum: n(C=O) 1680 cm . H NMR spectrum
(CDCl3, TMS), d, ppm: 1.18–1.32 m (3H), 1.80–2.00 m
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

74
LYSENKO, KULINKOVICH
9. Kochetkov, N.K., Likhosherstov,A.M., and Kritsyn, A.M.,
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