Cyclopropanation of alkynols with the CH2I2-R 3Al system

Article abstract of DOI:10.1007/s11172-011-0051-9

Acetylenic alcohols bearing two or three methylene groups between the triple bond and hydroxy group react with CH₂I₂ in the presence of trialkylalanes to give 1,1,2-tri- and 1,1,2,2-tetrasubstituted cyclopropanes.

Full text of DOI:10.1007/s11172-011-0051-9

Russian Chemical Bulletin, International Edition, Vol. 60, No. 2, pp. 313—318, February, 2011
313
Cyclopropanation of alkynols with the CH2I2—R3Al system
I. R. Ramazanov,a A. V. Yaroslavova,a U. M. Dzhemilev,a and O. M. Nefedovb
aInstitute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: iramazan@inbox.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328
Acetylenic alcohols bearing two or three methylene groups between the triple bond and
hydroxy group react with CH2I2 in the presence of trialkylalanes to give 1,1,2ꢀtriꢀ and 1,1,2,2ꢀ
tetrasubstituted cyclopropanes.
Key words: cyclopropanes, diiodomethane, alkynols, trialkylaluminums, aluminum
carbenoids.
The development of new approaches to the synthesis
of cyclopropane compounds is an important task of orꢀ
ganic chemistry. We have found earlier that dialkyl(iodoꢀ
methyl)aluminums generated in situ from CH2I2 and triꢀ
alkylalanes react with acetylenes to form cyclopropane
compounds,1—7 and the nature of substituent at the triple
bond substantially affect the direction of the reaction. In
this process alkylꢀ and phenylꢀsubstituted acetylenes form
triꢀ and tetrasubstituted cyclopropanes,2,6 whereas propꢀ
argyl alcohols produce exclusively bisꢀcyclopropane deꢀ
rivatives5 (Scheme 1).
dichloromethane at room temperature for 24 h followed by
deuterolysis of the reaction mixture afforded 1ꢀ(2ꢀdeuterꢀ
oxyethyl)ꢀ1ꢀethylꢀ2ꢀpentylꢀ2ꢀ(2ꢀdeuteroethyl)cycloꢀ
propane (1b) in 68% yield.
Scheme 2
Scheme 1
Comꢀ
pound
1a
1b
1c
R
Alk
Comꢀ
pound
1e
1f
1g
R
Alk
R1 = alkyl; R2 = alkyl, Ph, H; Alk = Et, Bui
Bun
nꢀC5H11
nꢀC12H25
Bun
Et
Et
Et
nꢀC5H11
nꢀC8H17
nꢀC12H25
Me
Me
Me
The purpose of the present work was to study the deꢀ
pendence of the direction of the reaction of acetylenic
alcohols with an Alk3Al—CH2I2 mixture (usually the moꢀ
lar ratio acetylene : Alk3Al : CH2I2 was 1 : 6 : 4) on the
distance between the hydroxyl and acetylenic groups,
which made it possible to develop the general method of
conversion of functionally substituted acetylenes to comꢀ
pounds of the cyclopropane series.
1d
Me
Reagents and conditions: i. CH2I2 (4 equiv.), Alk3Al (6 equiv.),
CH2Cl2, 20 °C; ii. D2O.
One may judge about the structure of an intermediate
organoaluminum compound (OAC) from the structure of
the product of its deuterolysis (it is difficult to interpret the
correlation spectra of OAC because of ligand exchange
processes between the aluminum atoms). To identify comꢀ
Preliminary experiments showed that the reaction of
nonꢀ3ꢀynꢀ1ꢀol with CH2I2 and Et3Al (Scheme 2) in
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 306—311, February, 2011.
1066ꢀ5285/11/6002ꢀ313 © 2011 Springer Science+Business Media, Inc.

314
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
Ramazanov et al.
pound 1b, we used standard methods of 2D NMR spectroꢀ
scopy (COSY, HSQC, HMBC, NOESY).
formed due to the Al—I exchange between cyclopropylꢀ
containing OAC and CH2I2 (see Ref. 6). Probably, in the
case of homopropargyl alcohols, intramolecular coordiꢀ
nation prevents this exchange (Scheme 3).
However, in the case of octꢀ3ꢀynꢀ1ꢀol, with an inꢀ
crease in the amount of CH2I2 introduced into the reacꢀ
tion to the ratio acetylene : CH2I2 : Me3Al = 1 : 8 : 6 the
equilibrium can be shifted toward the formation of organoꢀ
iodine derivative 2 in 52% yield (see Scheme 3).
Thus, unlike propargyl alcohols, homopropargyl alcoꢀ
hols form tetrasubstituted cyclopropane structures similar
to those observed earlier in the reaction with nonfunctionꢀ
alized acetylenes.
We believe that the initial steps of the reaction are
analogous in both cases (with propargyl and homopropargyl
alcohols). Dialkyl(iodomethyl)aluminum8 generated in situ
carboaluminates acetylenic alcohol to form iodineꢀ
containing alkenylalane A (see Ref. 9 and Scheme 4). Subꢀ
sequent rearrangement involving trialkylalane affords unꢀ
saturated OAC B. The subsequent cyclopropanation
of the double bond10 affords cyclopropaneꢀcontaining
OAC С. In the case of propargyl alcohols, alumoxane is
eliminated to form vinylcyclopropane D. In the case of
homopropargyl alcohols, the elimination step is hindered
and methylene is inserted into the Al—C bond. The furꢀ
ther rearrangement of derivative E affords cyclopropaneꢀ
containing OAC F, whose deuterolysis gives 1.
The cyclopropane fragment in the 1H NMR spectrum
of compound 1b is characterized by the AB system of two
hydrogen atoms at δС(3)H(A) 0.10 and at δС(3)H(B) 0.13
with the geminal spinꢀspin coupling constant (SSCC)
2JН,Н = 4.4 Hz (Fig. 1). In the HSQC experiment, these
protons correlate with the signal of the carbon atom at
δС(3) 23.99, while, in the НМВС experiment, it correꢀ
lates with the signals of the quaternary carbon atoms at
δС(1) 27.09 and at δС(2) 29.37, as well as with the correꢀ
sponding substituents at the cyclopropane ring.
The 13С NMR spectrum of compound 1b contains
only one set of signals, indicating stereoselective character
of the reaction. Unfortunately, we failed to unambiguousꢀ
ly determine the stereoconfiguration of the tetrasubstitutꢀ
ed cyclopropane formed from an analysis of the NOESY
spectrum.
After deuterolysis, the reactions of octꢀ3ꢀynꢀ1ꢀol and
dodecꢀ3ꢀynꢀ1ꢀol with CH2I2 and Et3Al afford tetrasubstiꢀ
tuted cyclopropanes 1a,c (see Scheme 2).
On going from Et3Al to Me3Al, the formation of the
corresponding products 1d—g proceeds more slowly, and
2—3 days are needed for completion of the reaction. It is
interesting that an analogous reaction of dialkylꢀsubstiꢀ
tuted acetylenes with a mixture of CH2I2 and Me3Al afꢀ
fords 2ꢀiodoethyl derivatives of cyclopropane, which are
Fig. 1. Numeration of atoms in the 1H and 13C NMR spectra of compounds 1a—g and 2—6.

Cyclopropanation of alkynols
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
315
Scheme 3
R = H, alkyl
The proposed mechanism is confirmed by the strucꢀ
ture of deuterated derivative 3, which was isolated in 15%
yield by the deuterolysis of intermediate OAC E, which
was obtained after 24 h in the reaction of octꢀ3ꢀynꢀ1ꢀol,
CH2I2, and Me3Al at the reactant ratio 1 : 4 : 6 (see
Scheme 4). An indirect proof for this mechanism is an
experiment involving phenylꢀsubstituted homopropargyl
alcohol, 4ꢀphenylbutꢀ3ꢀynꢀ1ꢀol, which reacts with Me3Al
and CH2I2 followed by deuterolysis and affords individual
1,1ꢀdisubstituted cyclopropane 4 in 60% yield (Scheme 5).
We obtained an analogous product when involved methylꢀ
phenylacetylene in the reaction under study.6
According to Scheme 4, the structure of the product
formed is determined in the step of addition of dialkylꢀ
Scheme 4
R = alkyl, Alk = Et, Me
3: R = Bun, Alk = Me

316
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
Ramazanov et al.
Scheme 5
Table 1. The values of charges q(C) and q(C*) on the carꢀ
bon atoms of the triple bond in acetylenes R1—C≡C*—R2
calculated by the B3LYP/6ꢀ31G* method
R1
R2
q(C)
q(C*)
a.u.
nꢀBu CH2O(←AlMe3)AlMe2
nꢀBu (CH2)2O(←AlMe3)AlMe2
0.04
0.0
–0.02
–0.24
–0.08
–0.04
0.0
Ph
(CH2)2O(←AlMe3)AlMe2
(CH2)3O(←AlMe3)AlMe2
H
–0.02
Note. Occupancies of molecular orbitals are analyzed by
the NBO method.
tramolecular coordination of the aluminum atom with the
oxygen atom in intermediate A. Charge separation beꢀ
tween the spꢀhybridized carbon atoms is insignificant in
phenylꢀsubstituted acetylene and, most likely, the coorꢀ
dination effect determines regioselectivity of the carboꢀ
alumination step. The character of triple bond polarizaꢀ
tion in pentꢀ4ꢀynꢀ1ꢀol is opposite to that in alkylꢀsubstiꢀ
tuted acetylenic alcohols, thus favoring the addition of
the aluminum atom to the terminal carbon atom of the
acetylene bond.
To check this assumption, we involved pentꢀ4ꢀynꢀ1ꢀol
in the reaction with CH2I2 and Et3Al in dichloroꢀ
methane. The deuterolysis of the reaction mixture gave
substituted cyclopropane 5 in 56% yield (Scheme 6).
Using Me3Al instead of Et3Al and increasing the amount
of CH2I2 involved in the reaction to the ratio
acetylene : CH2I2 : Me3Al = 1 : 8 : 6, we succeeded to obꢀ
tain iodineꢀcontaining 1,1ꢀdisubstituted cyclopropane 6
in 35% yield. In the COSY spectrum, the doublet of the
Reagents and conditions: i. CH2I2 (4 equiv.), Me3Al (6 equiv.),
CH2Cl2, 20 °C, 48 h; ii. D2O.
(iodomethyl)aluminum to acetylene, i.e., it depends
on regioselectivity of carboalumination of acetylenic alꢀ
cohol. It is known that the carboalumination of acetylenes
proceeds through the fourꢀcentered transition state11 in
which the metal atom is coordinated to the carbon atom
of the triple bond having the highest πꢀelectron density.
Therefore, the NBO analysis of occupancies of molecular
orbitals was performed for a series of acetylenic compounds
by the B3LYP/6ꢀ31G* method (Table 1).
According to the data obtained (see Table 1), in
nꢀbutylꢀsubstituted alcohols bearing one or two methylꢀ
ene groups between the acetylenic and hydroxyl functions,
the maximum electron density is localized on the carbon
atom at the functionally substituted group. In addition,
the formation of one regioisomer can be favored by inꢀ
Scheme 6
Reagents and conditions: i. CH2I2 (4 equiv.), Et3Al (6 equiv.); ii. D2O; iii. CH2I2 (8 equiv.), Me3Al (6 equiv.); iv. H2O.

Cyclopropanation of alkynols
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
317
0.89 (t, 3 Н, С(12)Н3, J = 7.2 Hz); 0.90 (t, 2 Н, С(7)Н2D,
J = 7.6 Hz); 0.92 (t, 3 Н, С(14)Н3, J = 7.6 Hz); 1.21—1.50
(m, 6 Н, С(2)Н2, C(8)Н2, C(11)Н2); 1.38—1.46 (m, 2 Н, С(10)Н2);
1.40—1.52 (m, 4 Н, С(6)Н2, C(13)Н2). 13С NMR, δ: 10.81 (С(7),
J = 19.05 Hz); 11.04 (С(14)); 14.11 (С(12)); 22.73 (С(11));
23.99 (С(3)); 24.60 (С(6)); 24.86 (С(13)); 26.64 (С(2)); 27.09
(С(1)); 29.37 (С(9)); 30.53 (С(10)); 32.42 (С(8)); 37.56 (С(4));
61.59 (С(5)).
methyl group has a crossꢀpeak with the multiplet of the
hydrogen atom at C(5), which interacts in turn with the
methylene group of the iodomethyl fragment. The HMBC
spectrum additionally exhibits the interaction between the
methyl group and the C(1) atom of the cyclopropane ring.
Thus, the results obtained undoubtedly have synthetic
prospects and the approach based on analysis of charge
separation in the starting acetylenes is not rigid but qualiꢀ
tatively correctly describes regioselectivity of carboalumiꢀ
nation of disubstituted acetylenes.
1ꢀ(2ꢀDeuteroxyethyl)ꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ2ꢀdodecylꢀ1ꢀethylꢀ
cyclopropane (1c). Transparent oily liquid. The yield was 62%,
Rf = 0.58. Found (%): C, 78.97. C21H40D2O. Calculated (%):
1
C, 80.70. H NMR, δ: 0.05—0.2 (m, 2 Н, С(3)Н2); 0.85—1.0
(m, 8 Н, С(7)Н2D, С(19)Н3, C(21)Н3); 1.2—1.35 (m, 23 Н,
С(6)На, С(8)На, С(9)Н2—C(18)Н2, С(20)На); 1.35—1.5 (m, 3 Н,
С(6)Нb, С(8)Нb, С(20)Нb); 1.6—1.8 (m, 2 Н, С(4)Н2); 3.65—3.75
(m, 2 Н, С(5)Н2). 13С NMR, δ: 10.8 (С(7), J = 19.5 Hz); 11.22
(С(21)); 14.12 (С(19)); 22.69 (С(18)); 23.99 (С(20)); 24.54
(С(6)); 24.86 (С(3)); 26.99 (С(14)); 29.35 (С(9)); 29.65 (С(10));
29.68 (С(11)); 61.61 (С(5)); 29.74 (С(12)); 29.74 (С(13)); 29.74
(С(15)); 29.74 (С(16)); 30.59 (С(17)); 31.92 (С(8)); 33.56 (С(4)).
1ꢀButylꢀ1ꢀ(2ꢀdeuteroethyl)ꢀ2ꢀ(2ꢀdeuteroxyethyl)ꢀ2ꢀmethylꢀ
cyclopropane (1d). Transparent oily liquid. The yield was 71%,
Rf = 0.6. Found (%): C, 77.15. C12H22D2O. Calculated (%):
Experimental
Commercially available reagents were used. Prior to use
CH2Cl2 was distilled above P2O5. GLC analysis was performed
on a Carlo Erba chromatograph (Ultraꢀ1 glass capillary column
(Hewlett Packard) 25000×0.2 mm, flameꢀionization detector,
temperature of the thermostat during temperature programming
50 → 170 °С, helium as a carrier gas). Mass spectra were meaꢀ
sured on a Finnigan 4021 instrument (electron impact ionization
energy 70 eV, temperature of the ionization chamber 200 °С).
Elemental analysis was carried out on a Carlo Erba analyzer,
model 1106. 1Н and 13С NMR spectra were recorded on a Bruker
Avance 400 spectrometer (100 MHz (13С) and 400 MHz (1H)),
using SiMe4 and signals of residual protons of CDCl3 as internal
standards. The yields of products were determined by GC using
an internal standard. Thin layer chromatography was carried out
on Silufol UVꢀ254 plates in an ethyl acetate—petroleum ether
(1 : 4) system. Nonempirical calculations were performed using
the GAMESS program.12
Cyclopropanation of alkynols (general procedure). A 25ꢀmL
glass reactor was successively loaded on cooling to 0 °C and
stirring under argon with CH2Cl2 (5 mL), alkynol (2 mmol),
Alk3Al (12 mmol), and CH2I2 (0.64 mL, 8 mmol). The reaction
mixture was stirred at room temperature for a specified time
(24 h in the synthesis of 1а—с, 3, and 5 or 2 days in the synthesis
of 1d—g and 4). Then the mixture was cooled to 0 °C and D2O
(3 mL) was added. Precipitated aluminum deuteroxide was filꢀ
tered off. The aqueous layer was extracted with diethyl ether,
and the extract was combined with the organic layer, dried with
anhydrous CaCl2, and concentrated in vacuo. Individual prodꢀ
ucts (1a—g, 3, 4, and 5) were isolated by chromatography on
a column with silica gel using an EtOAc—petroleum ether
(1 : 10 → 1 : 3) system as an eluent.
1
C, 77.35. H NMR, δ: 0.05—0.3 (m, 2 Н, С(3)Н2); 0.85—1.0
(m, 5 Н, С(7)Н2D, С(11)Н3); 1.11 (s, 3 Н, С(12)Н3); 1.2—1.8
(m, 10 Н, С(4)Н2, C(6)Н2, C(8)Н2—C(10)Н2); 3.74 (t, 2 Н,
С(5)Н2, J = 6.8 Hz). 13С NMR, δ: 11.07 (С(7), J = 19.0 Hz);
14.16 (С(11)); 19.84 (С(12)); 23.19 (С(10)); 24.40 (С(6)); 25.10
(С(3)); 29.13 (С(9)); 31.10 (С(8)); 38.64 (С(4)); 61.64 (С(5)).
1ꢀ(2ꢀDeuteroxyethyl)ꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ1ꢀmethylꢀ2ꢀpentylꢀ
cyclopropane (1e). Transparent oily liquid. The yield was 75%,
Rf = 0.53. Found (%): C, 77.16. C13H24D2O. Calculated (%):
1
C, 77.93. H NMR, δ: 0.05—0.3 (m, 2 Н, С(3)Н2); 0.85—0.95
(m, 5 Н, С(7)Н2D, С(12)Н3); 1.12 (s, 3 Н, С(13)Н3); 1.15—1.55
(m, 10 Н, С(6)Н2, C(8)Н2—C(11)Н2); 1.67 (t, 2 Н, С(4)Н2,
J = 7.2 Hz); 3.76 (t, 2 Н, С(5)Н2, J = 7.2 Hz). 13С NMR, δ:
10.82 (С(7), J = 20.0 Hz); 14.12 (С(12)); 19.88 (С(13)); 22.70
(С(11)); 24.42 (С(6)); 25.11 (С(3)); 26.56 (С(9)); 31.37 (С(8));
32.40 (С(10)); 38.67 (С(4)); 61.69 (С(5)).
1ꢀ(2ꢀDeuteroxyethyl)ꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ1ꢀmethylꢀ2ꢀoctylꢀ
cyclopropane (1f). Transparent oily liquid. The yield was 83%,
Rf = 0.43. Found (%): C, 80.21. C16H30D2O. Calculated (%):
1
C, 79.27. H NMR, δ: 0.05—0.2 (m, 2 Н, С(3)Н2); 0.85—0.95
(m, 5 Н, С(7)Н2D, С(15)Н3); 1.11 (s, 3 Н, С(16)Н3); 1.2—1.8
(m, 18 Н, С(4)Н2, C(6)Н2, C(8)Н2—C(14)Н2); 3.7—3.8 (m, 2 Н,
С(5)Н2). 13С NMR, δ: 11.05 (С(7), J = 19.5 Hz); 14.19 (С(15));
19.72 (С(16)); 22.53 (С(14)); 24.48 (С(6)); 25.13 (С(3)); 27.08
(С(10)); 29.45 (С(11)); 29.66 (С(12)); 30.19 (С(9)); 31.42 (С(8));
31.96 (С(13)); 38.64 (С(4)); 61.75 (С(5)).
1ꢀButylꢀ1ꢀ(2ꢀdeuteroethyl)ꢀ2ꢀ(2ꢀdeuteroxyethyl)ꢀ2ꢀethylcyꢀ
clopropane (1a). Transparent oily liquid. The yield was 63%,
Rf = 0.40. Found (%): C, 77.26. C13H24D2O. Calculated (%):
1
C, 77.93. H NMR (СDCl3), δ: 0.05—0.20 (m, 2 Н, С(3)Н2);
1ꢀ(2ꢀDeuteroxyethyl)ꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ2ꢀdodecylꢀ1ꢀmethylꢀ
cyclopropane (1g). Transparent oily liquid. The yield was 80%,
Rf = 0.55. Found (%): C, 78.14. C20H38D2O. Calculated (%):
0.8—1.1 (m, 8 Н, С(7)Н2D, С(11)H3, С(13)H3); 1.15—1.8
(m, 7 Н, С(6)На, С(8)На, С(9)Н2, C(10)Н2, С(12)На); 1.9—2.1
(m, 3 Н, С(6)Нb, С(8)Нb, С(12)Нb); 2.3—2.4 (m, 2 Н, С(4)Н2);
3.55—3.8 (m, 2 Н, С(5)Н2). 13С NMR (СDCl3), δ: 10.81 (С(7),
J = 19.03 Hz); 11.22 (С(13)); 14.18 (С(11)); 23.98 (С(3)); 24.53
(С(12)); 24.86 (С(6)); 29.23 (С(9)); 29.43 (С(10)); 30.03 (С(8));
39.74 (С(4)); 61.59 (С(5)).
1ꢀ(2ꢀDeuteroxyethyl)ꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ1ꢀethylꢀ2ꢀpentylꢀ
cyclopropane (1b). Transparent oily liquid. The yield was 68%,
Rf = 0.63. Found (%): C, 77.98. C14H26D2O. Calculated (%):
C, 78.44. 1H NMR, δ: 0.10—0.13 (m, 2 Н, С(3)Н2, J = 4.4 Hz);
1
C, 80.46. H NMR, δ: 0.05—0.2 (m, 2 Н, С(3)Н2); 0.85—0.95
(m, 5 Н, С(7)Н2D, С(19)Н3); 1.11 (s, 3 Н, С(20)Н3); 1.2—1.35
(m, 22 Н, С(6)На, С(8)На, С(9)Н2—C(18)Н2); 1.4—1.55
(m, 2 Н, С(6)Нb, С(8)Нb); 1.6—1.75 (m, 2 Н, С(4)Н2); 3.7—3.8
(m, 2 Н, С(5)Н2). 13С NMR, δ: 11.01 (С(7), J = 19.3 Hz); 14.12
(С(19)); 19.85 (С(20)); 22.69 (С(18)); 24.42 (С(6)); 25.11 (С(3));
26.89 (С(14)); 29.35 (С(16)); 29.65 (С(15)); 29.68 (С(13)); 29.70
(С(11)); 29.70 (С(12)); 30.19 (С(10)); 31.92 (С(17)); 31.34
(С(8)); 31.42 (С(9)); 38.63 (С(4)); 61.68 (С(5)).

318
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
Ramazanov et al.
1ꢀButylꢀ1ꢀ(2ꢀdeuteromethylꢀ4ꢀdeuteroxybutꢀ2ꢀyl)cyclopropꢀ
1H NMR, δ: 0.29—0.46 (m, 4 Н, С(2)Н2, C(3)Н2); 1.08 (d, 3 Н,
С(9)Н3, J = 6.8 Hz); 1.29 (m, 1 Н, С(6)Нa); 1.40 (m, 1 Н,
С(4)Н); 1.51 (m, 2 Н, С(7)Н2); 1.57 (m, 1 Н, С(6)Нb); 3.09
(m, 1 Н, С(5)Нa); 3.39 (m, 1 Н, С(5)Нb); 3.61 (t, 2 Н, С(8)Н2,
J = 6.0 Hz). 13С NMR, δ: 10.47 (С(2)); 11.27 (С(3)); 12.71 (С(5));
17.63 (С(9)); 23.16 (С(1)); 28.64 (С(6)); 29.89 (С(7)); 43.16
(С(4)); 63.19 (С(8)).
ane (3). Transparent oily liquid. The yield was 15%, Rf = 0.62.
Found (%): C, 78.11. C12H22D2O. Calculated (%): C, 77.35.
1H NMR, δ: 0.22 (t, 2 Н, С(11)На, С(12)На, J = 5.2 Hz); 0.41
(t, 2 Н, С(11)Нb, С(12)Нb, J = 5.2 Hz); 0.83 (s, 5 Н, С(9)H2D,
С(10)Н3); 0.90 (t, 3 Н, С(8)Н3, J = 7.2 Hz); 1.05—1.15 (m, 2 Н,
С(6)Н2); 1.2—1.3 (m, 2 Н, С(7)Н2); 1.45—1.55 (m, 2 Н,
С(5)Н2); 1.70 (t, 2 Н, С(2)Н2, J = 7.6 Hz); 3.76 (t, 2 Н, С(1)Н2,
J = 7.6 Hz). 13С NMR, δ: 6.94 (2 C, С(11), C(12)); 14.15 (С(8));
23.51 (С(7)); 25.06 (t, С(9), J = 20 Hz); 25.38 (С(10)); 28.95
(С(6)); 32.19 (С(5)); 43.28 (С(2)); 60.12 (С(1)).
3ꢀDeuteromethylꢀ3ꢀdeuteroxyꢀ3ꢀ(1ꢀphenylcyclopropyl)butꢀ
ane (4). Transparent oily liquid. The yield was 60%, Rf = 0.6.
Found (%): C, 81.03. C14H18D2O. Calculated (%): C, 81.50.
1H NMR, δ: 0.64—0.88 (m, 4 Н, С(9)Н2, С(9´)Н2, АА´ВВ´
system); 0.87 (s, 6 Н, С(10)Н3, С(11)Н3); 1.56 (t, 2 Н, С(2)Н2,
J = 7.6 Hz); 3.79 (t, 2 Н, С(1)Н2, J = 7.6 Hz). 13С NMR, δ: 8.91
(2 C, С(9), C(9´)); 24.61 (С(10), J = 20 Hz); 24.90 (С(4)); 24.92
(С(11)); 28.05 (С(4)); 34.33 (С(3)); 43.33 (С(2)); 60.14 (С(1));
126.14 (С(8)); 127.32 (2 C, С(7), C(7´)); 144.92 (С(5)); 132.23
(2 C, С(6), C(6´)).
The authors are grateful to Prof. L. M. Khalilov, Head
of the Laboratory of Structural Chemistry of the Institute
of Petrochemistry and Catalysis, Russian Academy of Sciꢀ
1
ences, for help in recording and interpreting H and
13C NMR spectra.
This work was financially supported by the Ministry of
Science and Education of the Russian Federation (Progꢀ
ram for State Support of the Leading Scientific Schools of
the Russian Federation, Grant NShꢀ4105.2010.3) and the
Division of Chemistry and Materials Science of the Rusꢀ
sian Academy of Sciences (Program No. 1).
1ꢀ(2ꢀDeuteroethyl)ꢀ1ꢀ(3ꢀdeuteroxypropyl)ꢀ2ꢀethylcyclopropꢀ
ane (5). Transparent oily liquid. The yield was 56%, Rf = 0.51.
Found (%): C, 76.24. C10H18D2O. Calculated (%): C, 75.89.
1H NMR, δ: –(0.2—0.1) (m, 1 Н, С(3)На); 0.3—0.4 (m, 1 Н,
С(3)Нb); 0.4—0.5 (m, 1 Н, С(2)Н); 0.87 (t, 3 Н, С(8)Н3,
J = 7.2 Hz); 0.95 (t, 3 Н, С(10)Н3, J = 7.4 Hz); 0.9—1.05
(m, 1 Н, С(7)На); 1.25—1.5 (m, 5 Н, С(7)Нb, С(9)Н2, С(5)Н2);
1.5—1.7 (m, 2 Н, С(4)Н2); 3.64 (t, 2 Н, С(6)Н2, J = 6.6 Hz).
13С NMR, δ: 10.55 (С(8)); 14.48 (С(10)); 18.21 (С(3)); 22.35
(С(9)); 24.30 (С(1)); 25.84 (С(5)); 26.25 (С(2)); 30.07 (С(4));
30.19 (С(7)).
Synthesis of βꢀiodoethylꢀsubstituted cyclopropanes (general
procedure). A 25ꢀmL glass reactor was successively loaded on
cooling to 0 °C and stirring under argon with CH2Cl2 (5 mL),
alkynol (2 mmol), Ме3Al (12 mmol), and CH2I2 (1.28 mL,
16 mmol). The reaction mixture was stirred for 2 days at room
temperature and then cooled to 0 °C. Water (10 mL) was added
and aluminum hydroxide precipitated was filtered off. The furꢀ
ther treatment of the reaction mixture and isolation of the prodꢀ
uct were carried out analogously to the above described proceꢀ
dure of synthesis of substituted cyclopropanes.
References
1. I. R. Ramazanov, M. P. Luk´yanova, A. Z. Sharipova, A. G.
Ibragimov, U. M. Dzhemilev, O. M. Nefedov, Izv. Akad.
Nauk, Ser. Khim., 2001, 1338 [Russ. Chem. Bull., Int. Ed.,
2001, 50, 1406].
2. U. M. Dzhemilev, I. R. Ramazanov, A. G. Ibragimov, L. I.
Dyachenko, M. P. Lukyanova, O. M. Nefedov, J. Organoꢀ
met. Chem., 2001, 636, 91.
3. I. R. Ramazanov, L. K. Dilmukhametova, L. M. Khalilov,
U. M. Dzhemilev, O. M. Nefedov, Tetrahedron Lett., 2008,
49, 6058.
4. I. R. Ramazanov, L. K. Dil´mukhametova, U. M. Dzhemiꢀ
lev, O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim., 2009, 1311
[Russ. Chem. Bull., Int. Ed., 2009, 58, 1349].
5. I. R. Ramazanov, A. V. Yumagulova, U. M. Dzhemilev,
O. M. Nefedov, Tetrahedron Lett., 2009, 50, 4233.
6. I. R. Ramazanov, L. K. Dilmukhametova, U. M. Dzhemiꢀ
lev, O. M. Nefedov, J. Organomet. Chem., 2010, 695, 1761.
7. I. R. Ramazanov, A. V. Yaroslavova, L. M. Khalilov, U. M.
Dzhemilev, O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim.,
2010, 1623 [Russ. Chem. Bull., Int. Ed., 2010, 59, 1668].
8. D. B. Miller, Tetrahedron Lett., 1964, 17, 989.
9. H. Hoberg, Lieb. Ann. Chem., 1962, 656, 1.
1ꢀButylꢀ2ꢀ(2ꢀhydroxymethyl)ꢀ1ꢀ(2ꢀiodoethyl)ꢀ2ꢀmethylcycloꢀ
propane (2). Transparent oily liquid. The yield was 52%, Rf =
= 0.45. Found (%): C, 44.52; H, 7.01. C12H23IO. Calculatꢀ
1
ed (%): C, 46.46; H, 7.47. H NMR, δ: 0.22—0.28 (m, 2 Н,
10. K. Maruoka, Y. Fukutani, H. Yamamoto, J. Org. Chem.,
1985, 50, 4412.
С(3)Н2, AB system); 0.91 (t, 3 Н, С(11)Н3, J = 7.2 Hz); 1.13
(s, 3 Н, С(12)Н3); 1.24—1.35 (m, 4 Н, С(9)Н2, С(10)Н2);
1.28—1.42 (m, 2 Н, С(8)Н2); 1.67 (t, 2 Н, С(6)Н2, J = 7.2 Hz);
1.93—2.13 (m, 2 Н, С(4)Н2); 3.11—3.21 (m, 2 Н, С(5)Н2); 3.76
(t, 2 Н, С(7)Н2, J = 7.6 Hz). 13С NMR, δ: 2.93 (С(5)); 13.96
(С(11)); 19.93 (С(12)); 21.73 (С(2)); 22.97 (С(10)); 24.99(С(3));
29.57 (С(1)); 29.70 (С(9)); 31.07 (С(8)); 37.38 (С(4)); 38.39
(С(6)); 61.35 (С(7)).
11. J. J. Eisch, W. C. Kaska, J. Am. Chem. Soc., 1966, 88, 2976.
12. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert,
M. S. Gordon, J. J. Jensen, S. Koseki, N. Matsunaga, K. A.
Nguyen, S. Su, T. L. Windus, M. Dupuis, J. A. Montgomery,
J. Comput. Chem., 1993, 14, 1347.
1ꢀ(3ꢀHydroxypropyl)ꢀ1ꢀ(1ꢀiodopropꢀ2ꢀyl)cyclopropane (6).
Transparent oily liquid. The yield was 35%, Rf = 0.49. Found (%):
C, 40.80; H, 6.09. C9H17IO. Calculated (%): C, 40.31; H, 6.39.
Received May 17, 2010 ;
in revised form October 26, 2010