Nucleophilic cyclopropanation reaction with bis(iodozincio)methane by 1,4-addition to α,β-unsaturated carbonyl compounds

Article abstract of DOI:10.1002/asia.200900123

Treatment of α,β-unsaturated ketones with an electrophilic site at the γ-position in the presence of trimethyl-silyl cyanide with bis(iodozincio)me-thane afforded the (Z)-silyl enol ether of the β-cyclopropyl substituted ketone in good yields. The reactio

Full text of DOI:10.1002/asia.200900123

FULL PAPERS
DOI: 10.1002/asia.200900123
Nucleophilic Cyclopropanation Reaction with Bis(iodozincio)methane by
1,4-Addition to a,b-Unsaturated Carbonyl Compounds
Kenichi Nomura, Takaharu Hirayama, and Seijiro Matsubara*[a]
Abstract: Treatment of a,b-unsaturated
ketones with an electrophilic site at the
g-position in the presence of trimethyl-
silyl cyanide with bis(iodozincio)me-
thane afforded the (Z)-silyl enol ether
of the b-cyclopropyl substituted ketone
in good yields. The reaction proceeds
by 1,4-addition to form an enolate, and
its sequential intramolecular nucleo-
philic attack to an adjacent electrophil-
ic site. The reaction of g-ethoxycarbon-
yl-a,b-unsaturated ketone and bis(io-
dozincio)methane in the presence of
trimethylsilyl cyanide afforded 1-
ethoxy-1-trimethylsiloxycyclopropane
derivatives, which can be regarded as
the homoenolate equivalent. Addition-
ally, reaction of the obtained homoeno-
late equivalents with imines give 1-(E)-
alkenyl-2-(1-aminoalkyl)alkanols dia-
stereoselectively.
Keywords: cyclopropanation · dia-
stereoselectivity · enols · nucleo-
philic addition · silylation
Introduction
compounds. We have already shown that a sequential nucle-
ophilic reaction is an efficient route for cyclopropane ring
formation.[4] When 1,2-diketone 5, a,b-epoxyketone 6, or a-
sulfonyloxyketone 7 was treated with 1, 1,2-addition to the
carbonyl group proceeds to generate organozinc species, 8,
9, or 10, respectively. In this case, a sequential intramolecu-
lar nucleophilic attack of the carbon–zinc bond to another
carbonyl group or the leaving group, epoxy group, or sulfo-
nyloxy group, proceeds readily, and the corresponding zinc
alkoxide of cyclopropanol 11, 12, or 13 was obtained
(Scheme 2).
Many examples of 1,4-addition of an organozinc reagent to
a,b-unsaturated ketones have been reported.[1] We had also
reported that the gem-dizinc reagent undergoes 1,4-addition
to a,b-unsaturated ketones.[2] For example, treatment of
chalcone (2) with bis(iodozincio)methane (1) in the pres-
ence of chlorotrimethylsilane afforded (Z)-trimethylsilyl
enol ethers of b-iodozinciomethylketone 3 by 1,4-addition
(Scheme 1).[3] The sequential coupling reaction at the intro-
duced zinciomethyl group with other electrophiles, such as
phenyl iodide, was also possible in the presence of Pd0.
Instead of performing the intermolecular coupling shown
in Scheme 1, an intramolecular process would afford cyclic
In this context, we planned a sequential process of 1,4-ad-
dition and cyclopropane formation using gem-dizinc 1 to
produce a b-cyclopropyl substituted silyl enol ether. As
Scheme 1. 1,4-Addition of bis(iodozincio)methane (1) to chalcone (2)
and sequential coupling with phenyl iodide in the presence of Pd0.
[a] K. Nomura, T. Hirayama, Prof. S. Matsubara
Department of Material Chemistry
Graduate School of Engineering
Kyoto University
Kyoutodaigaku-katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)
Fax : (+81)75-383-2463
E-mail: matsubar@orgrxn.mbox.media.kyoto-u.ac.jp
Scheme 2. Nucleophilic cyclopropanation of bis(iodozincio)methane (1)
with 1,2-diketone (5), a,b-epoxyketone (6) or a-sulfonyloxyketone (7) by
iodozinciomethylation.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.200900123.
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Chem. Asian J. 2009, 4, 1298 – 1303

Scheme 3. Nucleophilic cyclopropanation of bis(iodozincio)methane (1)
by 1,4-addition.
Scheme 4. Cyclopropanation of g-acetoxy-a,b-unsaturated ketone 14a
with bis(iodozincio)methane (1).
shown in Scheme 3, we exam-
ined the treatment of a a,b-
unsaturated ketone carrying
an electrophilic site at the g-
position with bis(iodozincio)-
methane (1) in the presence
Table 1. Cyclopropanation of g-acyloxy-a,b-unsaturated ketone 14 with bis(iodozincio)methane (1) by 1,4-ad-
dition.
entry substrate
1
conditions
product
yield [%][a] d.r.[b]
of
a
silylation
reagent
(R3SiX).
258C, 3 h
86
–
–
–
Results and Discussion
2
258C, 3 h
83
A mixture of g-acetoxy-a,b-
unsaturated
(1.0 mmol),
ketone
triethylamine
14a
3
4
258C, 3 h
51[c]
(2.5 mmol), and trimethylsilyl
cyanide (2.2 mmol) in THF
was treated with 1 (1.2 mmol)
at 258C for 5 min. After
aqueous work-up, (Z)-silyl
enol ether of b-cyclopropyl
ketone 15a was obtained in
83% yield stereoselectively
(Scheme 4).[2,5]
Other examples are shown
in Table 1. In all cases, the
products were obtained as
(Z)-form enolates selectively.
0 to 258C, 12 h
80
80
75
59:41[d]
60:40
5
6
14e
À40 to 258C, 12 h 15e
0 to 258C, 12 h
0 to 258C, 12 h
0 to 258C, 12 h
15e
66:34
7
8
82
79:21[e]
85:15
27[f]
[a] Isolated yields. [b] The diastereomeric ratios were determined by 1H NMR. [c] 15d was obtained as equi-
molar mixture of (E)- and (Z)-isomers after purification. [d] The stereochemistry of substituents on cyclopro-
pane ring in major isomer was trans. See Supporting Information. [e] The diastereomeric ratio was determined
after converting to the corresponding ketone with 1 n aqueous HCl. [f] The starting material was recovered in
65% yield.
When
g-acetoxy-g-methyl-
a,b-enone 14e was treated
with 1 in the presence of tri-
methylsilyl cyanide, (Z)-eno-
late 15e was obtained in
80% yield with low diaste-
reoselectivity with respect to the stereochemistry of cyclo-
propane ring (entry 4). Starting the reaction at À408C did
not improve the diastereomeric ratio (entry 5). In these
cases, the diastereofacial selectivity of 1,4-addition to a,b-
enone will determine the diastereomeric ratio of the prod-
uct, because the subsequent intramolecular nucleophilic sub-
stitution of the remaining carbanion site to the adjacent acy-
loxy substituted carbon should be stereospecific. Yamamoto
has reported the diastereofacial selectivity of 1,4-addition of
carbon nucleophiles to a,b-unsaturated carbonyl deriva-
tives.[6] In general, the diastereoselectivity can be explained
by the modified Felkin–Anh model when 1,4-additions pro-
ceed through the Bꢁrgi–Dunitz trajectory[7] (Figure 1). The
model could be applied to our reaction, so the size of the
substituents at the g-position was examined to determine
the diastereoselectivity. The reaction of g-(2,4,6-trimethyl-
Abstract in Japanese:
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FULL PAPERS
Scheme 5. Cyclopropanation of ketoester 16a with bis(iodozincio)me-
thane (1).
Figure 1. Modified Felkin–Anh Model by Yamamoto.
benzoyloxy)-a,b-enone 14 f im-
Table 2. Cyclopropanation of ketoesters 16 with bis(iodozincio)methane (1).
proved the diastereomeric
ratio only slightly (entry 6). In
the case of g-isopropyl-substi-
tuted enone 14h, the diastereo-
meric ratio was improed to
85:15, but the reaction became
sluggish (entry 8).
entry
1
substrate
R’3SiX
product
yield(%)[a]
99
Me3SiCN
Instead of 14, g-ethoxycar-
bonyl-a,b-enone 16 was also
examined as
a substrate. A
2
Me3SiCN
73
mixture of ethyl (E)-3-benzoy-
lacrylate (16a, 1.0 mmol), trie-
thylamine (2.5 mmol), and tri-
methylsilyl cyanide (1.1 mmol)
in THF was treated with 1
(1.2 mmol) at 258C for 5 min.
Additional trimethylsilyl cya-
nide (1.1 mmol) was added and
the mixture was stirred for
10 min at room temperature.
After aqueous work-up, 1-
ethoxy-1-trimethylsiloxycyclo-
propane 17a was obtained in
99% yield (Scheme 5). The
configuration of the enolate
was the (Z)-form without any
diastereoselectivity from the
cyclopropane formation reac-
tion.
3
4
5
Me3SiCN
99
83
93
PhMe2SiCl
PhMe2SiCl
6
PhMe2SiCl
90
7
8
PhMe2SiCl
PhMe2SiCl
65
97
Other examples are shown
in Table 2. In all cases, the
products 17 were obtained as
an equimolar mixture of diaste-
reomers, as the intramolecular cyclopropanation proceeded
without diastereoselectivity (from 18 to 17 in Scheme 6).
When chlorodimethylphenylsilane was used as silylation re-
agent instead of trimethylsilyl cyanide, the corresponding
phenyldimethylsilyl ether derivatives 17a’–d’ were obtained
(entries 5–8).
[a] Isolated yields.
with Lewis acid generates homoenolates,[8] which can be ap-
[9]
À
plied for the C C bond forming reactions. When 17 was
activated by a Lewis acid, the homoenolate 19 would be
generated by cyclopropane ring opening (Scheme 7); the ho-
moenolate 19 is considered to be a 3-siloxyallylmetal spe-
cies.[10] This reagent might have an allylmetal form 19, be-
cause of the coordination between the metal and carbonyl
group. The silyl enol ether was formed as the (Z)-form se-
lectively. So, a nucleophilic reaction of 19 as 3-siloxyallylme-
The product 17 has
a 1-ethoxy-1-siloxycyclopropane
moiety, which is known to form an ester homoenolate by cy-
clopropane ring opening. Nakamura and Kuwajima had re-
ported that treatment of 1-siloxy-1-alkoxycyclopropanes
Scheme 7. Strategy of migration of iodozincio group from homoallyl
metal into allyl metal.
Scheme 6. Formation of cyclopropane 17 by 1,4-addition.
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Nucleophilic Cyclopropanation Reaction with Bis(iodozincio)methane
tal reagent was expected to
proceed regio- and diastereo-
selectively.[11]
Treatment of the tosylimine
of benzaldehyde with 17a in
the presence of zinc(II) iodide
gave the b-siloxylamine deriva-
tive 20a as a single diastereo-
mer (Scheme 8). The stereo-
chemistry of 20a was deter-
mined by X-ray analysis
(Figure 2).[12] Meanwhile, the
same reaction from 17a with-
out zinc(II) iodide resulted in
Scheme 9. Reaction of various imines with the homoenolate prepared from 16a.
a complete recovery.
4 h. As shown in Scheme 9, b-siloxylamine derivatives 20
were obtained with high diastereoselectivity. Instead of tosy-
limine, treatment of the phenylimine of benzaldehyde with
17a also gave the corresponding b-siloxylamine derivative
20 f diastereoselectively.
Scheme 8. The reaction of 17a as homoenolate with imine.
Instead of imines, other electrophiles were also examined.
Treatment of in situ formed 17a with propanal under the
reflux condition afforded the vic-diol 21 in moderate yield.
The product 21, however, was given as a diastereo mixture
(Scheme 10a). The reaction of acid anhydrides with 17a af-
forded a-(E)-alkenyl-a-siloxyketones 22 in good yields with
high (E)-selectivity (Scheme 10b).
We propose the explanation for the high diastereoselectiv-
ities in the reaction of imines with the homoenolate, as
shown in Figure 3. The conformation of the 3-siloxyallylzinc
intermediate might be fixed by the chelation between a zinc
atom and two oxygen atoms as (Z)-23a. The nucleophilic re-
action proceeds regioselectively, retaining the conformation,
and as a result, the product is afforded as the (E)-form dom-
inantly. Furthermore, considering the trajectory of nucleo-
phile to imine, we propose the reaction pathway shown as
24. In comparison with another possible intermediate 24’, 24
is much more favourable, since the intermediate 24’ contains
a steric interaction between an alkyl group on the imine and
a phenyl group in the reagent. In addition, an intermolecu-
lar chelation between a siloxy group and nitrogen atom of
Figure 2. The ORTEP of 20a.
When the ketoester 16a was treated with bis(iodozincio)-
methane (1) in the presence of trimethylsilyl cyanide as in
Scheme 5, zinc(II) salts such as zinc(II) iodide and cyanide
were also generated in situ. These zinc salts might mediate
the conversion of the 1-trime-
thylsiloxy-1-ethoxycyclopro-
pane moiety in 17a into the
zinc homoenolate. So we tried
the cyclopropantion reaction
and the addition reaction in
one pot without the isolation
of silyl ether 17a. For this pur-
pose, after the procedure for
the preparation of 17a from
16a without addition of trie-
thylamine, we added the tosyli-
mines and then raised the reac-
tion temperature to 808C for
Scheme 10. Reaction of propanal or acid anhydride with the homoenolate from 16a.
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S. Matsubara et al.
FULL PAPERS
(4 mL) was treated with bis(iodozincio)methane (1, 0.5m solution in
THF, 1.2 mmol) at 258C for 5 min. Additional trimethylsilyl cyanide
(1.1 mmol) was added and the mixture was stirred for 10 min at room
temperature. Triethylamine was added and the whole mixture was
poured into water, and the organic layer was extracted with hexane–
EtOAc. The combined organic layers were washed with brine, and dried
over Na2SO4. The solvent was removed under reduced pressure, and the
residue was purified by silica gel column chromatography to give the cor-
responding cyclopropane 17.
General procedure for the tandem reaction of bis(iodozincio)methane
(1), 13a, and imines: A mixture of (E)-ethyl 4-oxoalk-2-enoate (13,
1 mmol) and trimethylsilyl cyanide (1.1 mmol) in THF (4 mL) was treat-
ed with bis(iodozincio)methane (1, 0.5m solution in THF, 1.2 mmol) at
258C for 5 min. Additional trimethylsilyl cyanide (1.1 mmol) was added
and the mixture was stirred for 10 min at room temperature. A solution
of imine (1.2 mmol) in THF (1.5 mL) was added, and the resulting mix-
ture was heated to reflux for 4 h. The mixture was cooled to 08C and
poured into water to quench the reaction. The organic layer was extract-
ed with EtOAc. The combined organic layers were washed with brine
and dried over Na2SO4. The solvent was removed under reduced pres-
sure, and the residue was purified by silica gel column chromatography
to give the corresponding (E)-1-alkenyl-2-(1-aminoalkyl)alkanol 20.
Figure 3. Proposed conformation of (Z)-23 and the transition state 24.
the imine would benefit the intermediate 24. So, the nucleo-
philic attack of (Z)-23a to an imine proceeds via 24 to gen-
erate a couple of stereogenic centers diastereoselectively,
and as a result, the threo isomer 20a will be a major prod-
uct.
Conclusions
We have demonstrated the nucleophilic cyclopropanation
reaction of g-acyloxy-a,b-unsaturated ketone or g-ethoxycar-
bonyl-a,b-unsaturated ketone with bis(iodozincio)methane
in the presence of silylating reagent. The reaction proceeded
by 1,4-addition and sequential intramolecular nucleophilic
attack to adjacent electrophilic sites to afford cyclopropane
derivatives or 1-ethoxy-1-siloxycyclopropane derivatives in
good yield. Furthermore, we also demonstrated the reaction
with imines of (Z)-3-siloxyallylzinc species, which can be
prepared easily from the obtained 1-ethoxy-1-siloxycyclo-
propane derivative with the aid of zinc salts existing in the
reaction mixture. The reaction proceeded with high diaste-
reoselectivity to give 1-(E)-alkenyl-2-(1-aminoalkyl)alkanol.
Acknowledgements
This work was supported financially by the Japanese Ministry of Educa-
tion, Culture, Sports, Science and Technology, and by Kyoto University,
International Innovation Center. The authors acknowledge the support
by the Global COE Program “Integrated Materials Science” (#B-09).
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Experimental Section
Bis(iodozincio)methane (1): A mixture of Zn (25 mmol), diiodomethane
(1.0 mmol), and PbCl2 (0.01 mmol) in THF (2.0 mL) was sonicated for
1 h in an ultrasonic cleaner bath under Ar. To the mixture, diiodome-
thane (10 mmol) in THF (20 mL) was added dropwise over 15 min at
08C with vigorous stirring. The mixture was stirred for 2 h at 08C. After
the stirring was stopped, the reaction vessel was allowed to stand undis-
turbed for several hours. Excess zinc was separated by sedimentation.
1H NMR spectra of the obtained supernatant showed a broad singlet at
À1.2 ppm at 08C, which corresponded to the methylene proton of 1. The
supernatant was used for the further reaction as a solution of 1 in THF
(0.5–0.6m). Bis(iodozincio)methane in THF can be kept unchanged at
least for a month in a sealed reaction vessel.
General procedure for the nucleophilic cyclopropanation of g-acyloxy-
a,b-unsaturated ketone: A mixture of g-acyloxy-a,b-unsaturated ketone
(11, 1 mmol), triethylamine (2.5 mmol), and trimethylsilyl cyanide
(2.2 mmol) in THF (4 mL) was treated with bis(iodozincio)methane (1,
0.5m solution in THF, 1.2 mmol) at 258C for 3 h. Then, water was added
to quench the reaction and extracted with hexane. The combined organic
layers were washed with brine, and dried over Na2SO4. The solvent was
removed under reduced pressure, and the residue was purified by silica
gel column chromatography to give the corresponding cyclopropane 15.
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oxoalk-2-enoate: A mixture of (E)-ethyl 4-oxoalk-2-enoate (13, 1 mmol),
triethylamine (2.5 mmol), and trimethylsilyl cyanide (1.1 mmol) in THF
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13.608(13) ꢃ, b=110.316(15)8, V=1489(2) ꢃ3, Z=2, 1calcd
=
1.154 MgmÀ3, l
for 6267 reflections (I>2s(I)).
CATHNUGTREN(NUNG Moka)=0.71073 ꢃ, T=296 K, qmax =54.08, R=0.051
Received: March 31, 2009
Published online: June 16, 2009
Chem. Asian J. 2009, 4, 1298 – 1303
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1303