Cp2ZrCl2-Catalyzed cycloalumination of acetylenic alcohols and propargylamines by Et3Al

Article abstract of DOI:10.1007/s11172-011-0013-2

The Cp₂ZrCl₂-catalyzed cycloalumination of acetylenic alcohols and propargylamines by Et₃Al was studied. The process affords 2,3-disubstituted alumacyclopent-2-enes, which were identified by the analysis of the products of

Full text of DOI:10.1007/s11172-011-0013-2

Russian Chemical Bulletin, International Edition, Vol. 60, No. 1, pp. 99—106, January, 2011
99
Cp2ZrCl2ꢀCatalyzed cycloalumination of acetylenic alcohols
and propargylamines by Et3Al
I. R. Ramazanov, R. N. Kadikova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: iramazan@inbox.ru
The Cp2ZrCl2ꢀcatalyzed cycloalumination of acetylenic alcohols and propargylamines by
Et3Al was studied. The process affords 2,3ꢀdisubstituted alumacyclopentꢀ2ꢀenes, which were
identified by the analysis of the products of their deuterolysis and hydrolysis. The cycloalumiꢀ
nation of alkylꢀ and phenylꢀsubstituted propargylamines proceeds with high regioꢀ and stereoꢀ
selectivity to give the corresponding allylamine derivatives in high yield. Unlike the phenyl
derivatives, the cycloalumination of alkylꢀsubstituted acetylenic alcohols (propargyl, homoproꢀ
pargyl, and bishomopropargyl alcohols) is not regioselective.
Key words: organoaluminum compounds, alumacyclopentenes, cycloalumination, cyclic
carboalumination.
Among numerous methods of synthesis of organoaluꢀ
minum compounds, the reactions of hydroꢀ, carboꢀ, and
cycloalumination of olefins and acetylenes found the widꢀ
est use.1 However, the first two methods are well studied
both methodologically and theoretically, while cycloaluꢀ
mination is relatively new promising direction that reꢀ
quires the study of boundaries of application of this reacꢀ
tion and its mechanism. We have earlier2 reported the
synthesis of substituted alumacyclopentꢀ2ꢀenes from alkylꢀ
and phenylꢀsubstituted acetylenes. It was found3 that the
cycloalumination of nonsymmetric alkylꢀ, phenylꢀ, and
allylꢀsubstituted acetylenes by Et3Al affords regioisomeric
2,3ꢀdisubstituted alumacyclopentꢀ2ꢀenes, whose yield and
ratio depend on the nature of substituents in the starting
acetylenes.
of the reaction temperature to 40 °С and an increase in the
catalyst concentration to 20 mol.% favor the formation of
alumacyclopentꢀ2ꢀenes. In the case of alkylꢀsubstituted
propargyl alcohols (heptꢀ2ꢀynol, nonꢀ2ꢀynol), cycloaluꢀ
mination followed by deuterolysis affords deuterolysis
products 1a,b in 37 and 41% yields, respectively (Scheme 1).
The reaction occurs stereoselectively to form substituted
allyl alcohols of the Zꢀconfiguration. The cycloaluminaꢀ
tion of 3ꢀphenylpropꢀ2ꢀynol requires more rigid condiꢀ
tions and the use of 3 molar equivalents of Et3Al over
propargyl alcohol. However, the reaction product is formed
with high regioꢀ and stereoselectivity and in a higher yield
(60%) compared to alkylꢀsubstituted propargyl alcohols.
Scheme 1
In order to extend the area of application of the above
cycloalumination reaction and taking into account the
important role of various functional substituents in the
induction of biological activity, in the present work we
studied the regularities of the reaction with acetylenic
alcohols and amines.
Results and Discussion
Cycloalumination of propargyl alcohols. At room temꢀ
perature propargyl alcohols are not almost involved in
cycloalumination. For instance, in the reaction of heptꢀ2ꢀ
ynol with Et3Al (the mole ratio of the reactants is 1 : 3) in
hexane in the presence of 10 mol.% Cp2ZrCl2 at room
temperature, the conversion of the starting propargyl
alcohol after 24 h does not exceed 5%. However, the rise
R = Bu (1a), C6H13 (1b, 2a), Ph (1c, 2b)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 96—102, January, 2011.
1066ꢀ5285/11/6001ꢀ99 © 2011 Springer Science+Business Media, Inc.

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Ramazanov et al.
The structure of alumacyclopentꢀ2ꢀenes was estabꢀ
ate. In the case of alkylꢀsubstituted propargyl alcohols,
the reaction is not regioselective and affords, along with
alumacyclopentenes, a mixture of compounds, which are,
most likely, the dimerization products of allene. The latter
could be formed by the βꢀelimination of the Et2AlO group
in intermediate B.
lished by 1D and 2D NMR spectroscopy of the products
of their deuterolysis (1a—c) and hydrolysis (2a,b). The
reaction can afford regioꢀ and stereoisomers with different
positions of the substituents at the double bond. In the
1Н NMR spectrum of compounds 2a,b, the singlet charꢀ
acter of the methylene group of the hydroxymethyl moiety
indicates the geminal arrangement of the ethyl group toꢀ
ward the hydroxymethyl group and makes it possible to
unambiguously judge about the position of the hydroxyꢀ
methyl group, because for another possible regioisomer the
methylene group of the hydroxymethyl moiety should apꢀ
pear in the 1Н NMR spectrum as a doublet. The NOESY
spectrum of compound 1b distinctly shows the interaction
between the methylene group of the hydromethyl moiety
and the αꢀmethylene group of the nꢀhexyl substituent,
which indicates the cisꢀconfiguration of the substituted
allyl alcohol that formed. The cisꢀconfiguration of comꢀ
pound 1c, obtained by the deuterolysis of the cycloalumiꢀ
nation product of 3ꢀphenylpropꢀ2ꢀynol, is indicated by
the crossꢀpeak between the signals of the hydrogen atoms
of the phenyl group and the methylene group of the hydrꢀ
oxymethyl moiety in the NOESY spectrum.
Relatively low yield of the cycloalumination products
of alkylꢀsubstituted propargyl alcohols can be explained
by the nonꢀregioselective character of the reaction. Accorꢀ
ding to the previously proposed4 mechanism of cycloꢀ
alumination, regioisomeric intermediates A and B are
formed at one of the stages of the process (Scheme 2). It is
assumed with allowance for the known data5 that the
zirconocene—ethylene complex is formed upon the reꢀ
arrangement of the fiveꢀmembered bimetallic intermediꢀ
Cycloalumination of butꢀ3ꢀynol and pentꢀ4ꢀynol and
their derivatives. The results similar to those described
above were also obtained in the case of acetylenic alcohols
containing two or three methylene groups between the
acetylene and hydroxyl functions (butꢀ3ꢀynol, pentꢀ4ꢀ
ynol) and also for nꢀbutylꢀsubstituted homopropargyl
alcohol (Scheme 3). However, unlike the cycloaluminaꢀ
tion of alkylꢀsubstituted propargyl alcohols, no undesirꢀ
able rearrangement with the Et2AlO group elimination
occurs and a mixture of regioisomers in a ratio of ~1 : 1
is formed. The reaction is stereoselective and after deuꢀ
terolysis gives olefins 3—6 in high yield. The phenylꢀsubꢀ
stituted derivative of homopropargyl alcohol (4ꢀphenylꢀ
butꢀ3ꢀynol) predominantly forms one regioisomer, whose
structure was determined by NMR spectroscopy of
the products of deuterolysis 7 and hydrolysis 8. In the
NOESY spectrum, the crossꢀpeak between the signals of
the hydrogen atoms of the phenyl group and the methylꢀ
ene group С(2)H2 of the hydroxyethyl moiety indicates
the cisꢀconfiguration of compound 7. The singlet signal of
1
the hydrogen atom at the double bond in the H NMR
spectrum of hydrolysis product 8 unambiguously indiꢀ
cates the position of the phenyl group in the molecule,
since signal splitting should be observed for another regioꢀ
isomer due to the spinꢀspin interaction with the methylꢀ
ene group.
Scheme 2

Cycloalumination of alcohols and amines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
101
Scheme 3
R = H (3a, 4, 5a, 6), Bu (3b, 5b); n = 1 (3a,b, 5a,b), 2 (4, 6)
R = Ph, n = 1 (7, 8); R = SiMe3, n = 2 (9, 10)
Scheme 4
Interestingly, the cycloalumination of siliconꢀsubstiꢀ
tuted pentꢀ4ꢀynol (5ꢀtrimethylsilylpentꢀ4ꢀynol) also ocꢀ
curs with high regioselectivity, unlike the cycloaluminaꢀ
tion of unsubstitited pentꢀ4ꢀynol.
Cycloalumination of propargylamines. Continuing the
study of the catalytic cycloalumination of functionally subꢀ
stituted acetylenes and taking into account availability and
wide use of propargylamines in synthetic practice, we exꢀ
amined the regularities of cycloalumination of these comꢀ
pounds. It was found that, unlike alkylꢀsubstituted propꢀ
argyl alcohols, the cycloalumination of alkylꢀsubstituted
propargylamines is regioselective and occurs with high
yield. In addition, propargylamines demonstrate a conꢀ
siderably higher reactivity than propargyl alcohols. For
example, the interaction of N,Nꢀdimethylheptꢀ2ꢀynꢀ1ꢀ
amine with 2 equiv. Et3Al in the presence of 20 mol.%
Cp2ZrCl2 in hexane occurs within 2 h at 40 °C to form
(after deuterolysis) (2Z)ꢀ2ꢀdeuteroꢀ3ꢀ(2ꢀdeuteroethyl)ꢀ
N,Nꢀdimethylheptꢀ2ꢀenꢀ1ꢀamine (11a) in 83% yield
(Scheme 4). To determine the structure of 1ꢀethylꢀ2ꢀ(N,Nꢀ
dimethylaminomethyl)ꢀ3ꢀnꢀbutylalumacyclopentꢀ2ꢀene,
in addition to deuterolysis we carried out hydrolysis to
form substituted allylamine 12, whose triplet signal of the
vinylic hydrogen atom in the COSY spectrum has a crossꢀ
peak with the doublet of the methylene group of the N,Nꢀ
dimethylaminomethyl moiety.
R = Bu (a), C8H17 (b)
and the signals of the hydrogen atoms of the N,Nꢀdimethꢀ
ylaminomethyl group.
In addition, the NMR spectra for the complex of
1ꢀethylꢀ2ꢀ(N,Nꢀdimethylaminomethyl)ꢀ3ꢀnꢀbutylalumacyꢀ
clopentꢀ2ꢀene with THF (13) were measured. The HMBC
spectrum of complex 13 exhibits crossꢀpeaks between the
signals of the quaternary carbon atoms of the double bond
Thus, in the case of alkylꢀsubstituted propargylamines,
no undesirable rearrangement with functional group elimꢀ

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Ramazanov et al.
Scheme 5
ination occurs. It is most likely that this is due to a lower
electronegativity of the nitrogen atom compared to the
oxygen atom and a higher stability of the organozircoꢀ
nium intermediates because of the lower affinity to βꢀeliꢀ
mination (Scheme 5). Sixꢀmembered intermolecular comꢀ
plex С with the stronger donorꢀacceptor bond N→Al due
to a higher nucleophilicity of amines compared to alcoꢀ
hols can favor higher (compared to alkylꢀsubstituted proꢀ
pargyl alcohols) regioselectivity of the reaction.
the molecule occurs with the formation of zirconacycloꢀ
pentadiene, whose subsequent transmetallation in the catꢀ
alytic cycle and deuterolysis result in the bis(alkylidene)
derivative of cyclohexane 16 (Scheme 7). The NOESY
spectrum of product 16 shows the interaction of the methꢀ
ylene group of the N,Nꢀdimethylaminomethyl moiety with
the αꢀmethylene group of the cyclohexane ring, indicatꢀ
ing the Eꢀconfiguration of the double bonds. In the COSY
spectrum of hydrolysis product 17, the crossꢀpeak between
As in the case of acetylenic alcohols, the cycloalumiꢀ
nation of phenylꢀsubstituted propargylamine, viz., N,Nꢀ
dimethylꢀ3ꢀphenylpropꢀ2ꢀynꢀ1ꢀamine, is regioselective,
and the regioselectivity is opposite to that observed in the
reaction with alkylꢀsubstituted propargylamines (Scheme 6).
Scheme 7
Scheme 6
In the cycloalumination of N,N,N´,N´ꢀtetramethylꢀ
decaꢀ2,8ꢀdiyneꢀ1,10ꢀdiamine obtained by the aminomeꢀ
thylation of 1,7ꢀoctadiyne by bis(amine),6 ethylene is disꢀ
placed from the coordination sphere of the zirconium atom
and the reductive coupling of two acetylene moieties of

Cycloalumination of alcohols and amines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
103
Fig. 1. Numeration of carbon atoms used in the description of the 1H and 13C NMR spectra of the deuterolysis and hydrolysis products.
the triplet signal of the hydrogen atoms at the double bond
and the doublet of the methylene group at the nitrogen
atom indicates the geminal arrangement of the hydrogen
atom and the N,Nꢀdimethylaminomethyl group at the C
atom of the double bond. A similar formation of alkylꢀ
ideneꢀsubstituted cyclohexane has earlier7 been observed
for the cycloalumination of trimethyl(octꢀ7ꢀenꢀ1ꢀynꢀ1ꢀ
yl)silane.
tuted homopropargyl alcohol. The theoretical model
explaining the regioselectivity of cycloalumination and relꢀ
ative reactivity of the acetylenic compounds on the basis
of the quantum chemical calculations will be developed
elsewhere.
Experimental
Numeration of carbon atoms used in the description of
the NMR spectra of the deuterolysis and hydrolysis prodꢀ
ucts is shown in Fig. 1.
Commercially available reagents were used. The reactions
with the organoaluminum compounds were carried out in dried
argon. Hexane was distilled above Bui3Al. Substituted propargyl
alcohols were synthesized by the reaction of organomagnesium
acetylenes with paraform using the known procedure.8 Proparꢀ
gylamines were synthesized by the aminomethylation of termiꢀ
nal acetylenes by the described procedure.6 The reaction prodꢀ
ucts were analyzed on a Carlo Erba chromatograph (glass capilꢀ
lary column Ultraꢀ1 (Hewlett Packard) 25 m × 0.2 mm in size,
flameꢀionization detector, working temperature 50—170 °С, heꢀ
lium as a carrier gas). Mass spectra were measured on a Finnigan
4021 instrument with an ionizing electron energy of 70 eV, and
the temperature of the ionization chamber was 200 °С. Elemenꢀ
tal analysis was carried out on a Carlo Erba analyzer, model
1106. 1Н and 13C NMR spectra were recorded on a Bruker
Avance 400 spectrometer (400.13 (1H) and 100.62 MHz (13С))
using SiMe4 and CDCl3, respectively, as internal standards.
Yields of the products were determined by GC using an internal
standard; TLC was carried out on plates Silufol UVꢀ254 in an
AcOEt—hexane (1 : 5) system. Boiling points were determined
by Sivolobov´s method.9
Relative reactivity of the acetylenic compounds. Comꢀ
pared to monoꢀ and dialkylꢀsubstituted acetylenes (hexꢀ
1ꢀyne, decꢀ5ꢀyne), the cycloalumination of acetylenic alꢀ
cohols and amines is more difficult and requires more
rigid conditions. We carried out studies aimed at estabꢀ
lishing the relative reactivity of functionally substituted
acetylenes in the reaction under study. The kinetics of
transformations of hexꢀ1ꢀyne, decꢀ5ꢀyne, heptꢀ2ꢀynol,
octꢀ3ꢀynol, and heptꢀ2ꢀynyl(dimethyl)amine in the reacꢀ
tion with Et3Al (3 mol. equiv.) in the presence of Cp2ZrCl2
(20 mol.% over acetylene) in a hexane solution was studꢀ
ied at constant temperature (40 °С). It was found that the
reactivity of the acetylenic compounds decreases in the
series: hexꢀ1ꢀyne (krel ≈ 2.7) > decꢀ5ꢀyne (krel = 1) > heptꢀ
2ꢀynyl(dimethyl)amine (krel
≈ 0.5) > octꢀ3ꢀynol
(krel ≈ 0.2) > heptꢀ2ꢀynol (krel ≈ 0.1). Thus, alkylꢀsubstiꢀ
tuted propargyl alcohol manifests the lowest reactivity in
the studied reaction. As mentioned above for the descripꢀ
tion of the cycloalumination of substituted propargyl alcoꢀ
hols, the phenyl derivative is involved in the reaction more
difficultly, which is also characteristic of phenylꢀsubstiꢀ
Cycloalumination of alkylꢀsubstituted propargyl and homoproꢀ
pargyl alcohols and 5ꢀ(trimethylsilyl)pentꢀ4ꢀynꢀ1ꢀol (general proꢀ
cedure). A glass 50ꢀmL reactor placed in a water bath (40 °C,
argon atmosphere) was successively loaded with an acetylenic
compound (1 mmol), Cp2ZrCl2 (0.2 mmol, 0.058 g), hexane

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Ramazanov et al.
(5 mL), and Et3Al (3 mmoL), and the mixture was magnetically
stirred for 18 h at 40 °С.
C(8)H3, C(18)H3); 0.95—1.05 (m, 4 H, C(10)H2D, C(20)H2D);
1.25—1.40 (m, 8 H, C(6)H2, C(7)H2, C(16)H2, C(17)H2);
1.95—2.10 (m, 4 H, C(5)H2, C(15)H2); 2.25—2.40 (m, 4 H,
C(2)H2, C(12)H2); 3.55—3.65 (m, 4 H, C(1)H2, C(11)H2).
Deuterolysis and hydrolysis of alumacyclopentꢀ2ꢀenes (generꢀ
al procedure). Hexane (5 mL) was poured to alumacyclopentꢀ2ꢀ
ene synthesized by the above described procedure, and then 3 mL
of D2O (deuterolysis) or 5 mL of H2O (hydrolysis) was added
dropwise on cooling of the reactor in an iceꢀcold bath. The
precipitate formed was filtered off. The aqueous layer was exꢀ
tracted with diethyl ether, and the extract was joined with the
organic layer, stored above anhydrous CaCl2, and concentrated
in vacuo. Individual products were isolated on a column with
silica gel using an AcOEt—hexane (1 : 10 → 1 : 5) mixture as an
eluent.
1
13C NMR, δ: 12.65 (t, C(4), C(13), JC,D = 19.5 Hz); 14.01
(C(8), C(18)); 22.40, 22.87 (C(7), C(17)); 27.56, 29.48, 29.57,
30.11, 30.83, 31.25, 32.35, 33.51, 61.00, 62.69 (C(1), C(11));
118.03 (t, C(4), C(13), 1JC,D = 24.5 Hz); 126.79 (t, C(4), C(13),
1JC,D = 25 Hz); 136.34, 145 (C(3), C(14)).
Mixture of (1E)ꢀ1ꢀdeuteroꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ5ꢀdeuteroxyꢀ
pentꢀ1ꢀene (4) and (3E)ꢀ1,4ꢀdideuteroꢀ7ꢀdeuteroxyheptꢀ3ꢀene
(6). Transparent oily liquid. The yield was 78%, Rf 0.34
(AcOEt—hexane, 1 : 5). Found (%): C, 69.25. C7H11D3O. Calꢀ
culated (%): C, 71.74. 1H NMR, δ: 0.80—1.10 (m, 4 H, C(6)H2D,
C(12)H2D); 1.90—2.10 (m, 4 H, C(5)H2, C(11)H2); 2.26 (t, 2 H,
C(8)H2, J = 6.2 Hz); 2.32 (t, 2 H, C(2)H2, J = 6.4 Hz); 3.63
(t, 2 H, C(7)H2, J = 6.2 Hz); 3.72 (t, 2 H, C(1)H2, J = 6.4 Hz);
4.98 (s, 1 H, C(4)HD); 5.50—5.65 (m, 1 H, C(10)H). 13C NMR,
(3Z)ꢀ1,4ꢀDideuteroꢀ3ꢀ(deuteroxymethyl)octꢀ3ꢀene (1a). Transꢀ
parent oily liquid. The yield was 37%, Rf 0.37 (AcOEt—hexane,
1 : 5). Found (%): C, 74.12. C9H15D3O. Calculated (%): C, 74.42.
1H NMR, δ: 0.91 (t, 3 H, C(7)H3, J = 6.8 Hz); 1.03 (t, 2 H,
C(9)H2D, J = 7.4 Hz); 1.25—1.40 (m, 6 H, C(4)H2—C(6)H2);
2.05—2.20 (m, 4 H, C(4)H2, C(8)H2); 4.16 (s, 2 H, C(1)H2).
1
1
δ: 11.75 (t, C(7), JC,D = 19.1); 13.31 (t, C(14), JC,D = 19);
1
13C NMR, δ: 12.59 (t, C(9), JC,D = 19.4 Hz); 13.96 (C(7));
25.20 (C(13)); 28.49 (C(6)); 29.46 (C(10)); 30.60 (C(3)); 32.27
1
22.31 (C(6)); 27.10, 27.66 (C(4), C(8)); 32.27 (C(5)); 60.37
(C(1)); 139.75 (C(2)). MS, m/z (Irel (%)): 145 [M+] (1), 126
(18), 110 (29), 97 (33), 83 (31).
(C(9)); 61.83, 62.06 (C(1), C(8)); 107.38 (C(5), JC,D = 23.4);
128.09 (C(11), 1JC,D = 22.7); 138.09 (C(12)); 150.85 (C(4)).
[(1Z)ꢀ1ꢀDeuteroꢀ2ꢀ(2ꢀdeuteroethyl)ꢀ5ꢀdeuteroxypentꢀ1ꢀenꢀ
1ꢀyl](trimethyl)silane (9). Transparent oily liquid. The yield was
75%, Rf 0.32 (AcOEt—hexane, 1 : 5). Found (%): C, 62.97.
C10H19D3OSi. Calculated (%): C, 63.42. 1H NMR, δ: 0.10
(s, 9 H, SiMe3); 0.89 (t, 2 H, C(7)H2D, J = 6.4 Hz); 1.65—1.80
(m, 2 H, C(2)H2); 2.10—2.25 (m, 2 H, C(6)H2); 3.60—3.70
(m, 2 H, C(1)H2). 13C NMR, δ: 0.27 (3 C, C(8)—C(10)); 12.49
(t, С(7), J = 19 Hz); 28.83 (C(6)); 31.00 (C(2)); 34.36 (C(3));
63.87 (C(1)); 160.68 (C(4)).
(3Z)ꢀ1,4ꢀDideuteroꢀ3ꢀ(deuteroxymethyl)decꢀ3ꢀene (1b). Transꢀ
parent oily liquid. The yield was 41%, Rf 0.44 (AcOEt—hexane,
1 : 5). Found (%): C, 76.01. C11H19D3O. Calculated (%):
1
C, 76.24. H NMR, δ: 0.89 (t, 3 H, C(9)H3, J = 7.2 Hz); 1.05
(t, 2 H, C(11)H2D, J = 7.6 Hz); 1.20—1.40 (m, 8 H,
C(5)H2—C(8)H2); 2.07 (t, 2 H, C(4)H2, J = 7.2 Hz); 2.15 (t, 2 H,
C(10)H2, J = 7.6 Hz); 4.16 (s, 2 H, C(1)H2). 13C NMR, δ: 12.62
1
(t, C(11), JC,D = 19.5 Hz); 14.12 (C(9)); 22.65 (C(8)); 26.98,
30.13, 31.38 (C(5)—C(7)); 27.54 (C(4)); 27.84 (C(10)); 60.58
(C(1)); 127.19 (C(3)); 140.14 (C(2)).
(4Z)ꢀ4ꢀEthylꢀ5ꢀ(trimethylsilyl)pentꢀ4ꢀenꢀ1ꢀol (10). Transꢀ
parent oily liquid. The yield was 79%, Rf 0.3 (AcOEt—hexane,
1 : 5). Found (%): C, 63.92; H, 11.72. C10H22OSi. Calculatꢀ
(2Z)ꢀ2ꢀEthylnonꢀ2ꢀenꢀ1ꢀol (2a). Transparent oily liquid. The
yield was 47%, Rf 0.4 (AcOEt—hexane, 1 : 5). Found (%):
C, 77.67; H, 13.07. C11H22O. Calculated (%): C, 77.58; H, 13.02.
1H NMR, δ: 0.90 (t, 3 H, C(9)H3, J = 7.4 Hz); 1.05 (t, 3 H,
C(11)H3, J = 7.6 Hz); 1.20—1.40 (m, 8 H, C(5)H2—C(8)H2);
1.63 (br.s, 1 H, OH); 2.00—2.10 (m, 2 H, C(4)H2); 2.10—2.20
(m, 2 H, C(10)H2); 4.12 (s, 2 H, C(1)H2); 5.31 (t, 1 H, C(3)H,
J = 7.6 Hz). 13C NMR, δ: 12.94 (C(11)); 14.12 (C(9)); 22.66
(C(8)); 26.99, 30.15, 31.38 (C(5)—C(7)); 27.54 (C(4)); 27.85
(C(10)); 60.58 (C(1)); 127.15 (C(3)); 140.11 (C(2)).
1
ed (%): C, 64.45; H, 11.90. H NMR, δ: 0.10 (s, 9 H, SiMe3);
0.84 (t, 3 H, C(7)H3, J = 7.4 Hz); 1.50 (br.s, 1 H, OH); 1.60—1.80
(m, 2 H, C(2)H2); 2.10—2.20 (m, 2 H, C(6)H2); 3.60—3.70
(m, 2 H, C(1)H2); 3.66 (s, 1 H, C(5)H). 13C NMR, δ: 0.34 (3 C,
C(8)—C(10)); 12.74 (С(7)); 28.95 (C(6)); 31.11 (C(2)); 34.39
(C(3)); 63.94 (C(1)); 160.77 (C(4)).
Cycloalumination of 3ꢀphenylpropꢀ2ꢀynꢀ1ꢀol and 4ꢀphenylꢀ
butꢀ3ꢀynꢀ1ꢀol (general procedure). A 50ꢀmL glass reactor placed
in a water bath (40 °C, argon) was successively loaded with an
acetylenic compound (1 mmol), Cp2ZrCl2 (0.1 mmol, 0.029 g),
hexane (3 mL), and Et3Al (5 mmol). The mixture was magnetiꢀ
cally stirred for 24 h at 40 °С. The procedure of further treatment
of the reaction mixture and isolation of the product is similar to
that described above.
Mixture of (1Е)ꢀ1,4ꢀdideuteroꢀ2ꢀ(2ꢀdeuteroxyethyl)butꢀ1ꢀ
ene (3a) and (3Е)ꢀ1ꢀdeuteroxyꢀ3,6ꢀdideuterohexꢀ3ꢀene (5a).
Transparent oily liquid. The yield was 74%, Rf 0.3 (AcOEt—
hexane, 1 : 5). Found (%): C, 68.97. C6H9D3O. Calculated (%):
C, 69.85. 1H NMR, δ: 0.80—1.10 (m, 4 H, C(6)H2D, С(12)Н2D);
1.90—2.10 (m, 4 H, C(5)H2, C(11)H2); 2.26 (t, 2 H, C(8)H2,
J = 6.2 Hz); 2.32 (t, 2 H, C(2)H2, J = 6.4 Hz); 3.63 (t, 2 H, С(7)H2,
J = 6.2 Hz); 3.72 (t, 2 H, C(1)H2, J = 6.4 Hz); 4.98 (s, 1 H,
C(4)HD); 5.50—5.65 (m, 1 H, C(10)H). 13C NMR, δ: 11.91
[(1Z)ꢀ1,4ꢀDideuteroꢀ2ꢀ(deuteroxymethyl)butꢀ1ꢀenꢀ1ꢀyl]ꢀ
benzene (1c). Transparent oily liquid. The yield was 60%, Rf 0.35
(AcOEt—hexane, 1 : 5). Found (%): C, 80.32. C11H11D3O. Calꢀ
1
culated (%): C, 79.95. H NMR, δ: 1.17 (t, 2 H, C(11)H2D,
1
(t, C(6), JC,D = 20 Hz); 13.45 (t, C(12), 1JC,D = 19 Hz); 25.50
J = 7.2 Hz); 2.36 (t, 2 H, C(10)H2, J = 7.2 Hz); 4.31 (s, 2 H,
C(1)H2); 7.20—7.40 (m, 5 H, Ph). 13C NMR, δ: 12.46 (t, C(11),
1JC,D = 19.2 Hz); 29.09 (C(10)); 61.03 (C(1)); 126.63 (C(7));
128.20, 128.72 (4 C, C(5), C(6), C(8), C(9)); 137.28 (C(4));
142.83 (C(2)).
(2Z)ꢀ2ꢀEthylꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀol (2b). Transparent oily
liquid. The yield was 69%, Rf 0.35 (AcOEt—hexane, 1 : 5).
Found (%): C, 81.35; H, 8.74. C11H14O. Calculated (%):
C, 81.44; H, 8.70. 1H NMR, δ: 1.19 (t, 3 H, C(11)H3, J = 7.6 Hz);
(C(11)); 28.42 (C(5)); 35.79 (C(8)); 39.29 (C(2)); 60.40 (C(1));
1
62.03 (C(7)); 109.99 (C(4), JC,D = 25 Hz); 124.42 (C(9),
1JC,D = 25 Hz); 135.57 (C(10)); 147.64 (C(3)).
Mixture of (3Z)ꢀ1,4ꢀdideuteroꢀ3ꢀ(2ꢀdeuteroxyethyl)octꢀ3ꢀ
ene (3b) and (3Z)ꢀ3ꢀdeuteroꢀ4ꢀ(2ꢀdeuteroethyl)ꢀ1ꢀdeuteroxyoctꢀ
3ꢀene (5b). Transparent oily liquid. The yield was 61%, Rf 0.28
(AcOEt—hexane, 1 : 5). Found (%): C, 74.12. C10H17D3O.
Calculated (%): C, 75.41. 1H NMR, δ: 0.85—0.95 (m, 6 H,

Cycloalumination of alcohols and amines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
105
1.59 (br.s, 1 H, OH); 2.34 (q, 2 H, C(10)H2, J = 7.6 Hz); 4.32
(s, 2 H, C(1)H2); 5.32 (s, 1 H, C(3)H); 7.20—7.40 (m, 5 H, Ph).
13C NMR, δ: 12.75 (C(11)); 29.07 (C(10)); 61.05 (C(1)); 126.64
(C(7)); 128.20, 128.71 (4 C, C(5), C(6), C(8), C(9)); 137.25
(C(4)); 142.81 (C(2)).
C(1)H2, J = 6.8 Hz); 5.22 (t, 1 H, C(2)H, J = 6.8 Hz). 13C NMR,
δ: 12.73 (C(9)); 14.03 (C(7)); 22.84 (C(6)); 29.58 (C(8)); 30.31
(C(5)); 30.71 (C(4)); 45.15 (2 C, C(10), C(11)); 56.77 (C(1));
120.24 (C(2)); 141.26 (C(3)).
(2Z)ꢀ3ꢀDeuteroꢀ2ꢀ(2ꢀdeuteroethyl)ꢀN,Nꢀdimethylꢀ3ꢀphenylꢀ
propꢀ2ꢀenꢀ1ꢀamine (14). Transparent oily liquid. The yield was
60%, b.p. 111—115 °С (5 Torr). Found (%): C, 79.11; N, 6.68.
[(1Z)ꢀ1,4ꢀDideuteroꢀ2ꢀ(2ꢀdeuteroxyethyl)butꢀ1ꢀenꢀ1ꢀyl]ꢀ
benzene (7). Transparent oily liquid. The yield was 67%, Rf 0.26
(AcOEt—hexane, 1 : 5). Found (%): C, 80.55. C12H13D3O. Calꢀ
1
C13H17D2N. Calculated (%): C, 81.62; N, 7.32. H NMR, δ:
1
culated (%): C, 80.40. H NMR, δ: 1.15 (t, 2 H, C(12)H2D,
1.16 (t, 2 H, C(11)H2D, J = 7.2 Hz); 2.15 (s, 6 H, C(12)H3,
J = 7.2 Hz); 2.25 (t, 2 H, C(11)H2, J = 7.2 Hz); 2.65—2.75
(m, 2 H, C(2)H2); 3.75—3.95 (m, 2 H, C(1)H2); 7.20—7.50 (m, 5 H,
Ph). 13C NMR, δ: 12.55 (t, C(12), J = 19.2 Hz); 29.80 (C(11));
33.95 (C(2)); 61.03 (C(1)); 126.23 (C(8)); 128.21, 128.69 (C(6),
C(7), C(9), C(10)); 138.03 (C(5)); 140.48 (C(3)).
C(13)H3); 2.15—2.20 (m, 2 H, C(10)H2); 2.38 (s, 2 H, C(1)H2);
1
7.15—7.40 (m, 5 H, Ph). 13C NMR, δ: 12.59 (t, C(11), JC,D
=
= 19 Hz); 28.55 (C(10)); 45.43 (2 C, C(12), C(13)); 58.52
(C(1)); 126.91 (C(7)); 127.92, 129.13 (C(5), C(6), C(8), C(9));
131.69 (C(4)).
(3Z)ꢀ3ꢀEthylꢀ4ꢀphenylbutꢀ3ꢀenꢀ1ꢀol (8). Transparent oily
liquid. The yield was 75%, Rf 0.3 (AcOEt—hexane, 1 : 5).
Found (%): C, 81.69; H, 9.11. C12H16O. Calculated (%):
C, 81.77; H, 9.15. 1H NMR, δ: 1.16 (t, 3 H, C(12)H3, J = 7.2 Hz);
2.25 (q, 2 H, C(11)H2, J = 7.2 Hz); 2.70—2.80 (m, 2 H, C(2)H2);
3.60—3.80 (m, 2 H, C(1)H2); 6.46 (s, 1 H, C(4)H); 7.20—7.50
(m, 5 H, Ph). 13C NMR, δ: 12.86 (C(12)); 29.93 (C(11)); 33.98
(C(2)); 61.07 (C(1)); 126.23 (C(8)); 128.21, 128.71 (C(6), C(7),
C(9), C(10)); 138.10 (C(5)); 140.56 (C(3)).
Cycloalumination of substituted propargylamines (general
procedure). A 50ꢀmL glass reactor placed in a water bath (40 °C,
argon) was successively loaded with an acetylenic compound
(1 mmol), Cp2ZrCl2 (0.2 mmol, 0.058 g), hexane (5 mL), and
Et3Al (2 mmol). The mixture was magnetically stirred for 3 h at
40 °С. The procedure of further treatment of the reaction mixꢀ
ture is similar to that described above. Individual compounds
were isolated by distillation under reduced pressure.
(2Z)ꢀN,NꢀDimethylꢀ3ꢀphenylpentꢀ2ꢀenꢀ1ꢀamine (15). Transꢀ
parent oily liquid. The yield was 75%, b.p. 83—88 °С (1 Torr).
Found (%): C, 82.31; H, 10.06; N, 7.52. C13H19N. Calculatꢀ
1
ed (%): C, 82.48; H, 10.12; N, 7.40. H NMR, δ: 1.22 (t, 3 H,
C(11)H3, J = 7.4 Hz); 2.19 (s, 6 H, C(12)H3, C(13)H3);
2.10—2.20 (m, 2 H, C(10)H2); 2.43 (s, 2 H, C(1)H2); 6.48 (s, 1 H,
C(3)H); 7.10—7.40 (m, 5 H, Ph). 13C NMR, δ: 12.81 (C(11));
28.59 (C(10)); 45.51 (2 C, C(12), C(13)); 58.58 (C(1)); 126.06
(C(3)); 127.04 (C(7)); 127.95, 129.19 (C(5), C(6), C(8), C(9));
131.70 (C(4)).
(1E,2E)ꢀ1,2ꢀBis[1ꢀdeuteroꢀ2ꢀ(dimethylamino)ethylidene]ꢀ
cyclohexane (16). Transparent oily liquid. The yield was 81%,
b.p. 114—117 °С (1 Torr). Found (%): C, 75.31; N, 11.21.
1
C14H24D2N2. Calculated (%): C, 74.94; N, 12.49. H NMR, δ:
1.55—1.70 (m, 4 H, C(5)H2, C(6)H2); 2.15—2.30 (m, 16 H,
C(4)H2, C(7)H2, C(11)H3—C(14)H3); 3.19 (s, 4 H, C(1)H2,
C(10)H2). 13C NMR, δ: 26.51 (2 C, C(5), C(6)); 29.00 (2 C,
C(4), C(7)); 45.20 (4 C, C(11)—C(14)); 56.29 (2 C, C(1), C(10));
119.47 (t, 2 C, C(2), C(9), J = 23.5 Hz); 144.47 (2 C, C(3), C(8)).
(2E,2´E)ꢀ2,2´ꢀCyclohexaneꢀ1,2ꢀdiylidenebis(N,Nꢀdimethylꢀ
ethanamine) (17). Transparent oily liquid. The yield was 70%,
b.p. 110—115 °С (1 Torr). Found (%): C, 75.51; H, 11.66;
N, 12.72. C14H26N2. Calculated (%): C, 75.62; H, 11.79;
(2Z)ꢀ2ꢀDeuteroꢀ3ꢀ(2ꢀdeuteroethyl)ꢀN,Nꢀdimethylheptꢀ2ꢀenꢀ
1ꢀamine (11a). Transparent oily liquid. The yield was 83%, b.p.
91—93 °С (15 Torr). Found (%): C, 76.91; N, 7.03. C11H21D2N.
1
Calculated (%): C, 77.12; N, 8.18. H NMR, δ: 0.90 (t, 3 H,
C(7)H3, J = 6.8 Hz); 0.98 (t, 2 H, C(9)H2D, J = 7.2 Hz);
1.20—1.40 (m, 4 H, C(5)H2, C(6)H2); 1.95—2.10 (m, 4 H,
C(4)H2, C(8)H2); 2.21 (s, 6 H, C(10)H3, C(11)H3); 2.88 (s, 2 H,
1
N, 12.60. H NMR, δ: 1.55—1.70 (m, 4 H, C(5)H2, C(6)H2);
1
C(1)H2). 13C NMR, δ: 12.40 (t, C(9), JC,D = 19.3 Hz); 14.00
2.15—2.35 (m, 16 H, C(4)H2, C(7)H2, C(11)H3—C(14)H3); 2.93
(d, 4 H, C(1)H2, C(10)H2, J = 7.2 Hz); 5.48 (t, 2 H, C(2)H,
C(9)H, J = 7.2 Hz). 13C NMR, δ: 26.52 (2 C, C(5), C(6)); 29.05
(2 C, C(4), C(7)); 45.19 (4 C, C(11)—C(14)); 56.39 (2 C, C(1),
C(10)); 119.84 (2 C, C(2), C(9)); 144.57 (2 C, C(3), C(8)).
Complex of 1ꢀethylꢀ2ꢀ(N,Nꢀdimethylaminomethyl)ꢀ3ꢀnꢀbutylꢀ
alumacyclopentꢀ2ꢀene with THF (13). The cycloalumination of
N,Nꢀdimethylheptꢀ2ꢀynꢀ1ꢀamine was carried out according to
the procedure described above. After the end of the reaction,
hexane was distilled off from the reaction mixture under reduced
pressure. The mixture was placed in an ampule of the NMR
spectrometer under an argon flow, and 1 equiv. of THF (over
Et3Al) was added. To record NMR spectra, HSQC, COSY,
HMBC, and NOESY procedures and tolueneꢀd8 as an interꢀ
nal standard were used. 13C NMR, δ: 13.78 (C(13)); 22.77
(C(12)); 45.25 (2 C, C(8), C(9)); 67.18 (C(7)); 137.04 (C(1));
160.43 (C(2)).
(C(7)); 22.82 (C(6)); 29.40 (C(8)); 30.28 (C(5)); 30.69 (C(4));
45.23 (2 C, C(10), C(11)); 56.74 (C(1)); 120.34 (t, C(2), 1JC,D
= 23.5 Hz); 141.24 (C(3)). MS, m/z: 171 [M+].
=
(2Z)ꢀ2ꢀDeuteroꢀ3ꢀ(2ꢀdeuteroethyl)ꢀN,Nꢀdimethylundecꢀ2ꢀ
enꢀ1ꢀamine (11b). Transparent oily liquid. The yield was 88%,
b.p. 105—108 °С (1 Torr). Found (%): C, 79.11; N, 6.68.
1
C15H29D2N. Calculated (%): C, 79.22; N, 6.16. H NMR, δ:
0.89 (t, 2 H, C(13)H2D, J = 6.4 Hz); 1.01 (t, 3 H, C(11)H3,
J = 7.2 Hz); 1.25—1.45 (m, 12 H, C(5)H2—C(10)H2); 2.04
(t, 2 H, C(4)H2, J = 6.0 Hz); 2.15—2.30 (m, 2 H, C(12)H2); 2.22
(s, 6 H, C(14)H3, C(15)H3); 2.90 (s, 2 H, C(1)H2). 13C NMR, δ:
1
12.74 (t, C(13), JC,D = 19 Hz); 14.09 (C(11)); 22.66 (C(10));
28.49, 29.28, 29.52, 29.56, 29.78 (5 C, C(4)—C(8)); 30.58
(C(12)); 31.89 (C(9)); 45.27 (2 C, C(14), C(15)); 56.87 (C(1));
120.52 (t, C(2), 1JC,D = 24 Hz); 144.36 (C(3)).
(2Z)ꢀ3ꢀEthylꢀN,Nꢀdimethylheptꢀ2ꢀenꢀ1ꢀamine (12). Transꢀ
parent oily liquid. The yield was 85%, b.p. 85—87 °С (10 Torr).
Found (%): C, 77.72; H, 13.80; N, 8.41. C11H23N. Calculatꢀ
Kinetic study of the cycloalumination reaction. The above
described procedure of cycloalumination of alkylꢀsubstituted proꢀ
pargyl and homopropargyl alcohols was used. The temperature
of the bath was 40 °С. The hydrolysis products were analyzed by
GC 5, 10, 15, 30, 60, 90, 120, 180, 240, and 480 min after the
reactants were loaded. The relative rate constant of transformaꢀ
1
ed (%): C, 78.03; H, 13.69; N, 8.27. H NMR, δ: 0.92 (t, 3 H,
C(7)H3, J = 6.8 Hz); 1.02 (t, 2 H, C(9)H2D, J = 7.2 Hz);
1.25—1.40 (m, 4 H, C(5)H2, C(6)H2); 2.00—2.10 (m, 4 H,
C(4)H2, C(8)H2); 2.24 (s, 6 H, C(10)H3, C(11)H3); 2.93 (d, 2 H,

106
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Ramazanov et al.
tion (krel) was determined by the ratio of the halfꢀreaction time
of decꢀ5ꢀyne to the halfꢀreaction time of the acetylenic comꢀ
pound in the reaction under study.
4. U. M. Dzhemilev, A. G. Ibragimov, A. P. Zolotarev, R. R.
Muslukhov, G. A. Tolstikov, Izv. Akad. Nauk SSSR, Ser.
Khim., 1989, 207 [Bull. Acad. Sci. USSR, Div. Chem. Sci.
(Engl. Transl.), 1989, 38, 194].
This work was financially supported by the Ministry of
Science and Education of the Russian Federation (Grant
NShꢀ4105.2010.3).
5. E.ꢀI. Negishi, D. Y. Kondakov, D. Choueiry, K. Kasai,
T. Takahashi, J. Am. Chem. Soc., 1996, 118, 9577.
6. M. G. Shaibakova, I. G. Titova, A. G. Ibragimov, U. M.
Dzhemilev, Zh. Org. Khim., 2008, 1141 [Russ. J. Org. Chem.
(Engl. Transl.), 2008, 44, 1126].
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Received June 8, 2010;
in revised form November 3, 2010