Formation of 1-ethenylcyclopropanols involving Kulinkovich cyclopropanation and Peterson olefination of α-trimethylsilylesters

Article abstract of DOI:10.1055/s-2003-39899

Mercuric iodide catalyzed condensation of bis-silylketene acetals with benzaldehyde provided a 1:1 erythro and threo mixture of α-trimethylsilylesters. Only the threo adducts underwent titanium(IV)-mediated cyclopropanation and acid induced Peterson olefination to provide (Z)-1-ethenylcyclopropanols of considerable synthetic potential.

Full text of DOI:10.1055/s-2003-39899

LETTER
1155
Formation of 1-Ethenylcyclopropanols Involving Kulinkovich Cyclo-
propanation and Peterson Olefination of a-Trimethylsilylesters
F
ormation of 1-Eth
a
enylcyclop
m
ropanols ien Hazelard, Jean Ollivier, Renée Paugam, Jacques Salaün*
Laboratoire des Carbocycles, UMR 8615, Institut de Chimie Moléculaire et des Matériaux d’Orsay, Université de Paris-Sud, 91405 Orsay,
France
Fax +33(1)69156278; E-mail: jasalaun@icmo.u-psud.fr
Received 26 April 2003
R1
Abstract: Mercuric iodide catalyzed condensation of bis-silyl-
ketene acetals with benzaldehyde provided a 1:1 erythro and threo
mixture of a-trimethylsilylesters. Only the threo adducts underwent
titanium(IV)-mediated cyclopropanation and acid induced Peterson
olefination to provide (Z)-1-ethenylcyclopropanols of considerable
synthetic potential.
CH2SiMe3
Ti(Oi-Pr)4
R1CH2CH2MgBr
Me3SiCH2CO2Et
+
1
OH
2a R1=H (67%)
trans-2b
Et (56%)
R2
SiMe3
R1
R1
R2CHO
R2
Key words: condensation, elimination, ring closure, titanium,
neighbouring group effect
n-BuLi
- Me3SiOH
OH
OH
OH
4a, trans-4b
3a, trans-3b
Scheme 1
Functionalized cyclopropanes and particularly 1-vinylcy-
clopropanol derivatives provide building blocks of con-
siderable synthetic potential. They not only undergo
selective acid, base or thermally-induced C3→C4–8 ring
expansions,1 and fluoride ion-induced C3→C10,15,20 ring
enlargements2 but, their corresponding sulfonic esters
(e.g., mesylates, tosylates) form significant p- or s-1,1-
ethylene allylmetal complexes, which then undergo regio-
and diastereoselective nucleophilic3 or electrophilic sub-
stitutions.4 Syntheses of various frameworks and natural
products have demonstrated the outstanding usefulness of
these rearrangements and substitutions.1–5 Consequently,
ready accesses to these synthons are of crucial impor-
tance. Previously available from 1,3-dichloroacetone,6 a-
enone silylenol ethers,7 cyclopropanone hemiacetals,8 or
1-hydroxycyclopropanecarboxylic acids,9 these com-
pounds have been recently prepared from the titanium-
mediated cyclopropanation10 of ethyl 3,3-diethoxypro-
pionate followed by modified Knoevenagel condensation
with malonic acid under microwave irradiation,11 or of b-
haloesters followed by base-induced dehydrohalogena-
tion,12 which provided diastereoselectively pure trans-1-
alkenyl-2-alkylcyclopropanols. On the other hand, titani-
um-mediated cyclopropanation of homoallyl alk-2-
enoates furnished diastereomerically pure cis-1-(1-alke-
nyl)-2-(2-hydroxyethyl)cyclopropanols.13
yields, respectively. Then, condensation with an aldehyde
were expected to furnish the adducts 3a and trans-3b, and
after Peterson olefination14 the required 1-ethenylcyclo-
propanols 4a and trans-4b (Scheme 1).
However, upon treatment with n-butyllithium (1 equiv)
and benzaldehyde (1 equiv), 2a,b underwent elimination
of hydroxysilane to give non-isolated volatile products,
likely methylenecyclopropane derivatives,15 rather than
the expected adducts 3a,b.16 Moreover, attempts to per-
form previous O-protection of the cyclopropanols 2a,b
(e.g., DHP, PPTs) before condensation, led also to elimi-
nation products.
In order to overcome the problem of the instability of the
1-[(trimethylsilyl)methyl]cyclopropanols 2a,b revealed
by this investigation,17 we have first carried out tentative-
ly the condensation of a-(trimethylsilyl)acetate 1 with
benzaldehyde. A 8:2 diastereomeric mixture of (E)- and
(Z)-bis(trimethylsilyl)ketene acetals 5a (R3 = SiMe3) was
obtained in 60% yield, upon treatment of 1 with 1 equiv-
alent of lithium diisopropylamide (LDA, from 1.6 M n-
BuLi in hexane and diisopropylamine) in the presence of
TMSCl in THF at –78 °C. Then, HgI2 (4.4%) induced
condensation of the mixture of (E,Z)-5a with benzalde-
hyde in toluene provided in 90% yield, an unseparable 1:1
erythro and threo mixture of ethyl 3-phenyl-2-tri(methyl-
silyl)-3-(trimethylsilyloxy)propionate 6a and 7a.18
We report herein our investigations to form these attrac-
tive synthons, alternatively from the commercially avail-
able ethyl a-(trimethylsilyl)acetate 1. Thus, reaction of
acetate 1 with EtMgBr and n-BuMgBr (2.2 equiv) in the
presence of Ti(i-PrO)4 (0.1 equiv) following reported pro-
cedures,10d–12 gave the 1-(trimethylsilylmethyl)cyclopro-
panol 2a (R1 = H) and trans-2b (R1 = Et) in 67% and 56%
Otherwise, reaction of 1 with LDA and TBDMSCl led ex-
clusively to the (E)-t-butyldimethylsilylketene acetal 5b
(R3 = Sit-BuMe2) in 33% yield; while, in the presence of
hexamethylphosphoramide (HMPT) as co-solvent, fol-
lowing a reported procedure,19 the ketene acetal (Z)-5c
was formed exclusively, in 60% yield. HgI2 catalyzed
condensation of (E)-5b with benzaldehyde gave also in
Synlett 2003, No. 8, Print: 24 06 2003.
Art Id.1437-2096,E;2003,0,08,1155,1159,ftx,en;G09403ST.pdf.
© Georg Thieme Verlag Stuttgart · New York

1156
D. Hazelard et al.
LETTER
11a¢ (R1 = Et, R3 = H) was also observed. The configura-
tions of these cyclopropanols were determined from their
1H and 13C NMR spectra, in particular trans-11a dis-
played one tertiary cyclopropanic proton at d 0.17 ppm (t,
J = 5.37 Hz, 1 H).13
LDA, ClSiMe3
Me3Si
OR3
OEt
1
or LDA,
ClSit-BuMe2
(E,Z)-5a R3=SiMe3 (60%; de: 60%)
(E)-5b R3=Sit-BuMe2 (33%)
(Z)-5c R3=Sit-BuMe2 (60%)
Finally, O-desilylation and Peterson olefination were
achieved upon treatment of these cyclopropanols under
acidic conditions,21 e.g., with concentrated H2SO4 in THF
at –78 °C or with chlorotrimethylsilane in MeOH at room
temperature, to provide the 1-(Z)-styrylcyclopropanol 12
(R1 = H)22 in 50% and 76% yield, respectively, from 9a,
while the cis- or trans-2-ethyl-1-[(Z)-styryl] cyclopro-
panol 13 (R1 = Et) were obtained in 75% yield upon treat-
ment of the corresponding cis- or trans-11a with TMSCl
in MeOH. Indeed, comparison of the olefinic coupling
constants of 12 and 13 (J = 13 Hz), with the reported cou-
pling constants for the (E)-1-styrylcyclopropanol (J = 16
Hz),23 and for the (E)- and (Z)-1-(2-p-tolylethenyl)cyclo-
propanols (J = 16 Hz and 12 Hz, respectively),24 as well
as their respective olefinic chemical shifts, [doublets at d
5.70 ppm and 6.50 ppm for (Z)-12 and at 5.92 and 6.62
ppm for (E)-12],23 led to assign a (Z)-configuration for
their styryl double bond.
1
EtOOC
Ph
EtOOC
H
OR3
H
PhCHO
2
3
+
H
H
OR3
HgI2
Me3Si
Me3Si
Ph
threo-7a (45%)
threo-7b (35%)
erythro-6a (45%)
erythro-6b (35%)
Scheme 2
70% yield a 1:1 mixture of diastereomeric adducts eryth-
ro-6b and threo-7b, which were now readily separable by
HPLC. Therefore, as reported for (E,Z)-5a,18 the geome-
try of the double bond of (E)-5b has also been lost during
the condensation reaction; on the other hand, attempted
condensation of (Z)-5c under the same conditions led nei-
ther to erythro-6b nor to threo-7b (Scheme 2).
Titanium(IV)-mediated cyclopropanation10 of the 1:1 dia-
stereomeric mixture of erythro-6a and threo-7a by EtMg-
Br (2.2 equiv) in the presence of Ti(i-PrO)4 (0.2 equiv)
was expected to provide a mixture of cyclopropanols 8a
and 9a (R1 = H, R3 = SiMe3), which only differed in the
configuration of their 1-substituents. However, the reac-
tion performed in THF at room temperature for 4 h, gave
in 52% yield (based on the reactant) the single cyclo-
propanol 9a20a displaying in the 1H NMR spectrum of its
1-substituent [2-phenyl-1-(trimethylsilyl)-2-(trimethyl-
silyloxy)ethyl] two doublets at d 0.71 ppm and 5.33 ppm
[J(H1¢H2¢) = 4.95 Hz]; 9a was always accompanied by var-
ious amounts of the corresponding diol 9a¢ (R1, R3 = H)20b
arising from partial O-deprotection (oxygentrimethylsilyl
bond cleavage). The recovered unreacted bis-silylated ad-
duct disclosed the persistent 1H NMR signals of erythro-
6a, in particular a methylene signal at 4.08–4.26 ppm and
a coupling constant J(H2H3) = 10.7 Hz.18
As the acid-induced Peterson olefination was known to
entail anti elimination of hexamethyldisiloxane,25 the ex-
clusive formation of the cyclopropanols (Z)-12 and cis-
and trans-(Z)-13 led to assign a threo configuration for the
1-substituents as shown for 9a and 11a (Scheme 3). From
these results it must be concluded that the configurations
of adducts 6a and 7a had been previously assigned erro-
neously.18 Moreover, X-ray crystallographic analyses of
the solid diol 9a¢ (recrystallized from hexane) have con-
firmed a threo configuration for its 1-substituent.26 On the
other hand, upon treatment with one equivalent of tetrabu-
tylammonium fluoride (n-Bu4NF) in THF at room tem-
perature, 9b underwent only O-desilylation to give
exclusively the 1-[2-hydroxy-2-phenyl-1-(trimethyl-
silyl)ethyl]cyclopropanol 9a¢20b while, its reaction with
BF3·Et2O was ineffective (Scheme 4).
Likewise, titanium(IV)-mediated cyclopropanation of the
pure silylated adduct threo-7b (R3 = TBDMS), occurred
to provide in 60% yield the single cyclopropanol 9b [dis-
Titanium-mediated cyclopropanation of the b-hydroxyes-
ter derivatives 14 (X = THP, TBDMS; R = Me, Ph, 2-
naphthyl) by EtMgBr and n-BuMgBr has been recently
reported to provide in 54–65% yields, the cyclopropanols
15a (R1 = H) and diastereoselectively the cyclopropanols
trans-15b (R1 = Et; de:100%) (Scheme 5).13b Therefore,
the presence of the a-trimethylsilyl substituent appeared
1
playing in its H NMR spectrum two doublets at d 0.67
ppm and 5.38 ppm for which J(H1¢H2¢) = 3.40 Hz]; while
its isolated pure diastereomer erythro-6b appeared also
unreactive towards this cyclopropanation reaction, irre-
spective of the experimental conditions [number of equiv-
alents of Grignard reagents and of Ti(i-PrO)4, temperature
and time of reaction] (Scheme 3).
R1
R1
Otherwise, reaction of a 1:2 mixture of erythro-6a and
threo-7a with n-BuMgBr (2.2 equiv) and Ti(i-PrO)4 (0.2
equiv) in THF at room temperature, gave in 30% yield
(based on the reactant) a 1:1 mixture of cis- and trans-
2-ethyl-1-[2-phenyl-1-(trimethylsilyl)-2-(trimethylsilyl-
oxy)ethyl] cyclopropanols 11a (R1 = Et, R3 = SiMe3), sep-
arable by liquid chromatography (eluent pentane/diethyl
ether, 9:1), besides a 2:1 mixture of unreacted bissilylated
esters 6a and 7a. The formation of the corresponding diols
EtMgBr
or n-BuMgBr
HO
HO
and / or
Me3Si
9a R1=H, R3=SiMe3
Ph
OR3
H
Erythro-6a,b
+ threo-7a,b
H
H
OR3
H
Ti(Oi-Pr)4
Me3Si
Ph
8a R1=H, R3=SiMe3
8b R1=H, R3=TBDMS 9a' R1, R3=H
10a R1=Et, R3=SiMe3
(52%)
9b R1=H, R3=TBDMS (60%)
11a R1=Et, R3=SiMe3
(30%)
11a' R1=Et, R3=H
Scheme 3
Synlett 2003, No. 8, 1155–1159 ISSN 1234-567-89 © Thieme Stuttgart · New York

LETTER
Formation of 1-Ethenylcyclopropanols
1157
responsible for the surprising difference of reactivity ob-
served between the diastereomeric silylated adducts
erythro-6a,b and threo-7a,b and for the lack of stereo-
selectivity in these cyclopropanation reactions.
OX
R1
EtMgBr or n-BuMgBr
COOEt
R
R
Ti(Oi-Pr)4
OX
OH
15a R1=H (54%)
14 X=THP, TBDMS
R =Me, Ph, 2-Naphthyl
trans-15b
Et (65%;
de: 100%)
Scheme 5
This difference of reactivity towards the titanium-mediat-
ed cyclopropanation reaction which occurred between the
stereoisomers erythro-6a and threo-7a was amazing. Ap-
parently, it does not simply result from different steric
hindrances around the carboxylate moiety of these a-silyl-
esters. In order to elucidate this unexpected stereoselectiv-
ity, we have assumed that the reactivity of the silylated
esters 6a and 7a is controlled by the formation of the in-
termediate titanafurans A and B. Therefore, we have un-
dertaken computational studies of the transition structures
resulting from the approaches of these esters by the titana-
cyclopropane 16.10 Taking into account the three chiral
centers of A and B, calculations were carried out on the
four possible approaches leading to the diastereomers
SRR-17 and SSS-18 arising from erythro-6a, SRS-19 and
SSR-20 arising from threo-7a (Schemes 6 and Figure 1).
After determination of the chiral chain conformations of
the esters by molecular dynamics simulations (MM2 force
field type), all the structures were minimized by semi-em-
pirical ZINDO method.27 To confirm our model, Hessian
calculations were carried out for each case and resulted in
a transition structure, i.e., in a first-order saddle point with
the Hessian having one negative eigenvalue.
Figure 1
lylketene acetals 5a,b with benzaldehyde, followed by
acid induced Peterson olefination can provide 1-[1-(Z)-
alkenyl]cyclopropanols 12 and cis- or trans-13; however,
this three-membered ring formation appeared highly de-
pendant on the configurations of the intermediate a-tri-
methylsilylester adducts 6a,b and 7a,b.
The differences in energies between these four structures,
DE = 3.1, 7.2, 0, and 9.0 kcal mol–1, respectively, appeared
consequently in full agreement with the difference of re-
activity observed between the adducts erythro-6a and
threo-7a, in this titanium(IV) induced cyclopropanation.
In conclusion, the titanium(IV)-mediated cyclopropana-
tion by Grignard reagents of a-trimethylsilylesters arising
from mercuric iodide catalyzed condensation of bissi-
3
2
4
OEt
5
(i-PrO)2Ti
Ph
SiMe3
R1
R1
O
erythro-6a
+
+
Ti(Oi-Pr)2
H
H
1
H
Ph
H
OSiMe3
16
Me3Si
Ph
OR3
A
OH
3
OH
4
5
12 (R1=H; 50%)
12 (76%)
cc H2SO4, THF
9a
9a
cis-11a
OEt
2
(i-PrO)2Ti
OSiMe3
ClSiMe3, MeOH, rt
threo-7a
O
Ti(Oi-Pr)2
cis-13 (R1=Et; 75%
1 H
Me3Si
H
trans-13 (R1=Et; 75%
16
trans-11a
Ph
n-Bu4NF
9b
B
9a' (100%)
Scheme 4
Scheme 6
Synlett 2003, No. 8, 1155–1159 ISSN 1234-567-89 © Thieme Stuttgart · New York

1158
D. Hazelard et al.
LETTER
(17) The cyclopropanol 2a (R1 = H) was previously isolated as
3,5-dinitrobenzoate from the alkylation-cyclization of ethyl
3-bromopropionate by Me3SiCH2MgBr/SmI2, see:
References
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(18) (a) Dicker, I. B. J. Org. Chem. 1993, 51, 2324. (b) In this
article (ref.18a) the J(threo) > J(erythro) relationship for the
H2H3 coupling constants, was erroneously based on the
consideration of stronger intramolecular hydrogen bonds in
the threo comparatively to the erythro adducts, see: House,
H. O.; Crumrine, D. S.; Teranishi, A. Y.; Olmstead, H. D. J.
Am. Chem. Soc. 1973, 95, 3310. (c) However, there are no
intramolecular hydrogen bond in the O-silylated
diastereoisomers 6a,b and 7a,b. The coupling constants of
erythro-6a [J(H2H3) = 10.7 Hz] and of threo-7a [J(H2H3) =
10.4 Hz] were carefully measured by peak pickings.
(19) Colvin, E. W. In Silicon Reagents in Organic Synthesis;
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(20) To a solution of 4 g (11 mmol) of the 1:1 mixture of ethyl 3-
phenyl-2-(trimethylsilyl)-3-(trimethylsilyloxy)propionate
erythro-6a and threo-7a in 15 mL of THF containing 0.62 g
(2.2 mmol; 0.2 equiv) of Ti(i-PrO)4 was added dropwise a
2.54 M solution of ethylmagnesium bromide (11 mL, 27
mmmol; 2.5 equiv) in diethyl ether within 4 h. The reacting
mixture was cooled to 0 °C (iced-water bath), then diluted
with diethyl ether and hydrolyzed with 10 mL of aq NH4Cl.
After filtration through celite, the separated organic layer
was washed with brine, dried on Na2SO4 and concentrated in
vacuo. Flash chromatography of the residue (eluant:
pentane/diethyl ether 9:1) gave two products:
(a) 1-[2-Phenyl-1-(trimethylsilyl)-2-(trimethylsilyl-
oxy)ethyl]cyclopropanol 9a: 1.94 g (52% yield); 1H NMR
(250 MHz, CDCl3) d –0.08 (s, 9 H), 0.71 (d, J = 4.95 Hz, 1
H), 0.25–0.88 (m, 4 H), 3.24 (s, 1 H), 5.33 (d, J = 4.95 Hz, 1
H), 7.19–7.33 (m, 5 H); 13C NMR (66 MHz, CDCl3): d 0.21,
0.28, 13.27, 15.62, 46.13, 58.92, 78.75, 126, 126.9, 127.9,
144.4; IR 3463, 3379, 2974, 2949 cm–1; MS m/z (EI) 322 (2)
[M+], 231 (42), 179 (31), 147 (17), 75 (36), 73 (100), 45 (16);
MS m/z (CI with NH3) 340 (0.1), 252 (17), 251 (61), 250
(100), 233 (40), 232 (44), 231 (74) 217 (18), 179 (21), 160
(21), 155 (15), 144 (26), 1433 (100).
(b) 1-(2-Hydroxy-2-phenyl-1-trimethylsilylethyl)cyclo-
propanol 9a¢: (various amounts 5–10%); white solid: mp 107
°C; 1H NMR (250 MHz, CDCl3) d –0.07 (s, 9 H), 0.76 (s, 1
H), 0.07–0.97 (m, 4 H), 2.58 (s, 1 H), 3.29 (s, 1 H), 5.44 (s,
1 H), 7.24–7.35 (m, 5 H); 13C NMR (66 MHz, CDCl3) d 0.32,
13.41, 16.02, 44.86, 59.97, 77.97, 125.17, 126.91, 128.09,
144.41; IR: 3468, 2955, 2898 cm–1; MS m/z (EI) 231 (33),
159 (33), 145 (16), 131 (33), 115 (12), 103 (16), 79 (27), 77
(44), 75 (93), 73 (100), 79 (27), 45 (26); MS m/z (CI with
NH3) 251 (19), 250 (81) [M+], 231 (10), 161 (16), 160 (13),
144 (13), 143 (100) 131 (8); Exact mass M+ 250.1377 (calcd
for C14H22SiO2 250.1389).
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(21) Base-induced Peterson olefination of cyclopropanols 9a and
11a led to ring-opened derivatives (see ref. 1).
(22) To a stirred solution of 340 mg (1 mmol) of cyclopropanol
9a in 5 mL of methanol at r.t. was added two drops of
chlorotrimethylsilane. The reaction was complete within 2 h,
as monitored by TLC. Then the solvent was removed in
vacuo; flash chromatography of the residue (eluant: pentane/
diethyl ether 9:1) gave 128 mg (76% yield) of 1-(Z)-styryl
cyclopropanol 12. 1H NMR (250 MHz, CDCl3) d 0.71–1.32
(m, 4 H), 2.16 (s, 1 H), 5.26 (d, J = 13 Hz, 1 H), 6.53 (d, J =
13 Hz, 1 H), 7.32–7.55 (m, 5 H); MS m/z (EI) 160 (41) [M+],
159 (74), 145 (54), 131 (68), 127 (36), 115 (43), 103 (63), 91
(33), 77 (100), 51 (52); MS m/z (CI with NH3) 178 (100),
161 (22), 160 (17), 159 (14), 143 (18), 131 (13).
Synlett 2003, No. 8, 1155–1159 ISSN 1234-567-89 © Thieme Stuttgart · New York

LETTER
Formation of 1-Ethenylcyclopropanols
1159
(23) Salaün, J.; Ollivier, J. Nouv. J. Chem. 1981, 5, 587.
(24) Ollivier, J. PhD Thesis; Université de Paris-Sud: Orsay
France, 1986.
(25) Colvin, E. W. In Silicon Reagents in Organic Synthesis;
Academic Press: New York, 1988, 65–69.
(27) Molecular mechanics calculations (using a MM+ force field)
and semi-empirical ZINDO calculations have been
performed with the Hyperchem software (version 5.1). The
Ti-O and Ti-C bond lengths and the Ti-bond angles were in
accord with reported RX data for titanium complexes. See:
Gais, H. J.; Volhardt, J.; Linder, H. J.; Paulus, H. Angew.
Chem., Int. Ed. Engl. 1988, 27, 1541.
(26) X-ray crystallographic data of the diol 9a¢, will be published
in Zeitschrift fuer Kristallographie.
Synlett 2003, No. 8, 1155–1159 ISSN 1234-567-89 © Thieme Stuttgart · New York