Cycloaddition of 2-pyridinetellurenyl chloride to alkenes

Article abstract of DOI:10.1007/s11172-012-0013-x

The action of 2-pyridinetellurenyl chloride on alkenes results in the polar cycloaddition of the tellurium-centered electrophile at the multiple bond with the formation of 2,3-dihydro[1,3]tellurazolo[3,2-a]pyridinium derivatives.

Full text of DOI:10.1007/s11172-012-0013-x

Russian Chemical Bulletin, International Edition, Vol. 61, No. 1, pp. 91—94, January, 2012
91
Cycloaddition of 2ꢀpyridinetellurenyl chloride to alkenes
A. V. Borisov,a Zh. V. Matsulevich,a V. K. Osmanov,a G. N. Borisova,a V. I. Naumov,a G. Z. Mammadova,b
A. M. Maharramov,b V. N. Khrustalev,c and V. V. Kachalad
aR. E. Alekseev Nizhny Novgorod State Technical University,
24 ul. Minina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 436 2311. Eꢀmail: avb1955@rambler.ru
bBaku State University,
23 ul. Z. Khalilova, AZ 1148 Baku, Azerbaijan Republic.
Fax: +994 (12) 598 3376. Eꢀmail: bsu@bsu.az
cA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: vkh@xray.ineos.ac.ru
dN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: vvk@ioc.ac.ru
The action of 2ꢀpyridinetellurenyl chloride on alkenes results in the polar cycloaddition of
the telluriumꢀcentered electrophile at the multiple bond with the formation of 2,3ꢀdiꢀ
hydro[1,3]tellurazolo[3,2ꢀa]pyridinium derivatives.
Key words: 2ꢀpyridinetellurenyl chloride, alkenes, polar cycloaddition, Xꢀray diffraction.
Scheme 1
Organyltellurenyl halides RTeHal are known for more
than half a century,1—7 however, in contrast to organylꢀ
sulfenylꢀ and organylselenenyl halides, addition of these
reagents to multiple bonds is studied poorly. In the literaꢀ
ture, there are only several examples of the reaction of
aryltellurenyl halides with unsaturated carboxylic acids,
which lead to the cyclization products with the ring closure
by the oxygen atom of the carboxyl group in the molecule
of unsaturated compound.8,9
Recently,10,11 we have synthesized 2ꢀpyridinetellureꢀ
nyl chloride (1), the first representative of hetarenetellureꢀ
nyl halides containing a nitrogenous base as a hetaryl subꢀ
stituent, and shown that its reaction with alkenes leads to
the heterocyclization products with the ring closure by the
nitrogen atom of the pyridine ring of the starting reagent.10
To clarify regioꢀ and stereochemistry, as well as a plauꢀ
sible mechanism of the heterocyclization found, in the
present work we studied reactions of tellurenyl chloride 1
with styrene (2a), tertꢀbutylethylene (2b), cyclopenꢀ
tene (2c), and norbornene (2d).
The reaction of tellurenyl chloride 1 with unsaturated
compounds 2a,b in dichloromethane at 20 C was found
to proceed regiospecifically to form the fused ring telluriꢀ
umꢀnitrogenꢀcontaining heterocycles 3a and 3b in 97 and
94% yields, respectively (Scheme 1).
R1 = Ph, R2 = H (a); R1 = H, R2 = But (b)
dition at the multiple bond, viz., the polycyclic systems 3c
and 3d in 92 and 95% yields, respectively (Scheme 2).
The structure of the synthesized compounds was inꢀ
ferred from the 1H and 13C NMR spectroscopic data and
confirmed by the elemental analysis data.
The signals in the 1H NMR spectra of compounds
3a—c were assigned based on the obtained earlier spectral
characteristics of cycloaddition products of hetarenesulfeꢀ
nyl chlorides to alkenes 2a—c, whose structure was conꢀ
firmed by Xꢀray crystallography.12—14
The structure of compound 3d was established by Xꢀray
diffraction studies (Fig. 1). Selected bond distances and
bond angles are given in Table 1.
The reaction of compound 1 with alkenes 2c,d under
the same conditions leads to the products of cisꢀcycloadꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 89—92, January, 2012.
1066ꢀ5285/12/6101ꢀ91 © 2012 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Borisov et al.
Table 1. Selected bond distances (d) and bond angles () in the
crystal of compound 3d
C(5)
C(9)
C(10)
C(8)
C(4)
C(3)
Bond
d/Å
Angle
/deg
C(13)
N(6)
Te(1)—C(1) 2.115(2)
Te(1)—C(12) 2.155(2)
C(1)—Te(1)—C(12)
Te(1)—C(1)—N(6)
C(1)—N(6)—C(7)
N(6)—C(7)—C(12)
81.85(7)
114.26(13)
120.54(15)
112.58(14)
C(7)
C(11)
C(1)—N(6)
N(6)—C(7)
1.355(2)
1.502(3)
C(2)
C(1)
C(12)
C(7)—C(12) 1.546(3)
Te(1)—C(12)—C(7) 110.40(12)
Te(1)
Compound 3d is a salt containing the pyridinium
cation and the chloride anion. The cation fragment Te(1)—
C(1)—C(2)—C(3)—C(4)—C(5)—N(6)—C(7)—C(12) is
virtually planar (an average deviation of the atoms from
the mean square plane is 0.04 Å). The tellurium atom
forms two additional short contacts with two chloride anꢀ
ions with the distances 3.078(1) and 3.343(1) Å, thus acꢀ
quiring a distorted planarꢀsquare coordination. This type
of interactions (Te...Hal) is characteristic of the large telꢀ
lurium atom, and not only in the lowꢀcoordination comꢀ
pounds (for the case of intermolecular interactions of
a dicoorditated tellurium atom with a chlorine atom, see
recent the works15—19). Cations and anions in the crystal
form chains along the axis b (Fig. 2) due to the existence
of these attractive interactions Te...Cl.
Cl(1)
Fig. 1. Molecular structure of compound 3d.
Scheme 2
The bicyclo[2.2.1]heptane fragment of the cation in
compound 3d has four asymmetric carbon atoms, C(7),
C(8), C(11), and C(12). The absolute configurations of
the indicated chiral centers are 7S,8R,11S,12R.
a
0
c
b
Fig. 2. Crystal packing of compound 3d.

Cycloaddition of pyridineꢀ2ꢀtellurenyl chloride
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
93
Earlier,12—14,20 when we studied the tandem addiꢀ
tion—cyclization processes in the reactions of hetareneꢀ
sulfenylꢀ and hetareneselenenyl chlorides with alkenes,
we found that the heterocyclization products with the ring
closure by a nucleophilic active center of the reagent hetaryl
fragment can be formed in two ways: the first way includes
the ring closure directly in the AdEꢀprocess; in the second
way, a cyclization product is formed as a result of intraꢀ
molecular nucleophilic substitution in ꢀchloro sulfides
or ꢀselenides (the initial reaction products). In this conꢀ
nection, we monitored the reactions of tellurenyl chloꢀ
ride 1 with alkenes 2a—d in deuterated dichloromethane
by 1H NMR spectroscopy. These experiments showed no
formation of the 1,2ꢀaddition products of tellurenyl chloꢀ
ride 1 to the multiple bond even in trace amount.
J = 7.3 Hz); 6.60 (t, 1 H, H(3), J = 7.3 Hz); 7.40 (m, 2 H, Ph);
7.48 (m, 3 H, Ph); 7.78 (dd, 1 H, H(6), J = 7.3 Hz, J = 5.9 Hz);
8.32 (t, 1 H, H(7), J = 7.3 Hz); 8.42 (d, 1 H, H(8), J = 7.3 Hz);
8.52 (d, 1 H, H(5), J = 5.9 Hz).
2ꢀ(tertꢀButyl)ꢀ2,3ꢀdihydro[1,3]tellurazolo[3,2ꢀa]pyridinꢀ4ꢀ
ium chloride (3b). The yield was 94%. Yellow crystals, m.p.
188—190 C. Found (%): C, 40.52; H, 4.87. C11H16ClNTe. Calꢀ
1
culated (%): C, 40.61; H, 4.96. H NMR, : 0.98 (s, 9 H, But);
4.44 (dd, 1 H, H(2), J = 7.3 Hz, J = 5.9 Hz); 5.16 (dd, 1 H, H(3),
J = 13.2 Hz, J = 7.3 Hz); 5.42 (dd, 1 H, H(3), J = 13.2 Hz,
J = 5.9 Hz); 7.81 (dd, 1 H, H(6), J = 7.3 Hz, J = 5.9 Hz); 8.27
(dd, 1 H, H(7), J = 8.8 Hz, J = 7.3 Hz); 8.35 (d, 1 H, H(8),
J = 8.8 Hz); 9.09 (d, 1 H, H(5), J = 5.9 Hz).
cisꢀ2,3,3a,9aꢀTetrahydroꢀ1Hꢀcyclopenta[4,5][1,3]tellurꢀ
azolo[3,2ꢀa]pyridinꢀ9ꢀium chloride (3c). The yield was 92%. Yelꢀ
low crystals, m.p. 135—137 C. Found (%): C, 38.68; H, 3.79.
1
C10H12ClNTe. Calculated (%): C, 38.84; H, 3.91. H NMR, :
In conclusion, the results obtained in this work allow
us to draw a conclusion that the formation of compounds
3a—d proceeds apparently by the scheme of polar cycloꢀ
addition,12,21—23 which includes involvement of the A type
intermediates (Scheme 3). Arising intermediates of this
type can be attributed to the specific features of the telluriꢀ
umꢀcontaining agent used, to be more specific, to the
presence of coordination bonds involving tellurium atꢀ
oms,2,3,7,11 which shields these atoms preventing their reꢀ
action with the neighboring carbocationic center.
1.70 (m, 2 H, CH2); 2.07 (m, 2 H, CH2); 2.24 (m, 1 H, CH2);
2.41 (m, 1 H, CH2); 4.65 (td, 1 H, H(3a), J = 8.0 Hz, J = 4.7 Hz);
5.78 (td, 1 H, H(9a), J = 8.5 Hz, J = 3.8 Hz); 7.75 (td, 1 H, H(7),
J = 6.2 Hz, J = 4.5 Hz); 8.22 (d, 2 H, H(5), H(6), J = 4.4 Hz);
8.97 (d, 1 H, H(8), J = 6.2 Hz).
exoꢀcisꢀ9ꢀTelluriumꢀ3ꢀazoniatetracyclo[9.2.1.02,10.03,8]ꢀ
tetradecaꢀ3(8),4,6ꢀtriene chloride (3d). The yield was 95%. Yelꢀ
low crystals, m.p. 230—232 C. Found (%): C, 42.88; H, 4.15.
1
C12H14ClNTe. Calculated (%): C, 42.99; H, 4.21. H NMR, :
1.34 (d, 1 H, Hsyn(14), J = 10.8 Hz); 1.39 (m, 1 H, H(12)); 1.52
(m, 1 H, H(12)); 1.68 (d, 1 H, Hanti(14), J = 10.8 Hz); 1.71
(m, 2 H, H(13)); 2.61 (s, 1 H, H(11)); 2.82 (s, 1 H, H(1)); 4.12
(d, 1 H, H(10), J = 8.4 Hz); 5.32 (d, 1 H, H(2), J = 8.4 Hz); 7.70
(dd, 1 H, H(5), J = 7.5 Hz, J = 6.2 Hz); 8.01 (dd, 1 H, H(6),
J = 8.0 Hz, J = 7.5 Hz); 8.20 (d, 1 H, H(7), J = 8.0 Hz); 8.93 (d, 1 H,
H(4), J = 6.2 Hz). 13C NMR, : 25.71 (C(12)); 29.41 (C(13));
31.84 (C(14)); 32.84 (C(10)); 45.97 (C(11)); 48.16 (C(1));
82.78 (C(2)); 123.99 (C(5)); 132.61 (C(7)); 141.45 (C(6));
145.22 (C(4)).
Scheme 3
Xꢀray diffraction studies of compound 3d. Parameters of a unit
cell and intensities of 17726 reflections were measured on a Bruker
SMART APEXꢀII CCD automatic threeꢀcircle diffractometer
(MoꢀKꢀirradiation, graphite monochromator, ꢀ and ꢀscan
Experimental
technique, 
= 32.7). For the data obtained, the absorption
max
of Xꢀray irradiation was applied using the SADABS program.24
The structure of compound 3d was solved by the direct method
and refined by the fullꢀmatrix least squares method in anisotroꢀ
pic approximation for nonhydrogen atoms. All the hydrogen
atoms, whose positions were calculated geometrically, were inꢀ
cluded into the refinement in isotropic approximation with the
fixed positional (the riding model) and thermal parameters. The
absolute configuration of the asymmetric atoms in compound 3d
was determined objectively through the refinement of the Fleck
parameter, which is equal to 0.116(15). A slightly overrated Fleck
parameter is explained by the specific (close to the centrosymꢀ
metric) arrangement of the heavy tellurium atoms. All the calꢀ
culations were performed using the SHELXTL program packꢀ
age.25 The crystals C12H14ClNTe at 100 K are orthorhombic,
1
H and 13C NMR spectra were recorded on a Bruker
Avanceꢀ600 spectrometer (600 and 150 MHz) in DMSOꢀd6.
Styrene (2a), tertꢀbutylethylene (2b), cyclopentene (2c), and
norbornene (2d) were purchased from Acros Organics (Belgium),
they were used freshly distilled. Dichloromethane was purified
by distillation over P2O5.
Reaction of 2ꢀpyridinetellurenyl chloride 1 with unsaturated
compounds 2a—d (general procedure). A solution of unsaturated
compound 2a—d (1 mmol) in dichloromethane (10 mL) was
added to a suspension of tellurenyl chloride 1 (0.24 g, 1 mmol) in
dichloromethane (10 mL) at 20 C with stirring. The solvent was
evaporated in vacuo 24 h after the complete dissolution of telꢀ
lurenyl chloride. Compounds 3a—d were obtained after recrysꢀ
tallization of the residue from dichloromethane.
a = 9.3956(3) Å, b = 9.7605(3) Å, c = 12.9619(4) Å, V =
3
3ꢀPhenylꢀ2,3ꢀdihydro[1,3]tellurazolo[3,2ꢀa]pyridinꢀ4ꢀium
chloride (3a). The yield was 97%. Yellow crystals, m.p.
172—174 C. Found (%): C, 45.11; H, 3.45. C13H12ClNTe. Calꢀ
culated (%): C, 45.22; H, 3.50. 1H NMR, : 3.80 (dd, 1 H, H(2),
J = 10.3 Hz, J = 7.3 Hz); 4.28 (dd, 1 H, H(2), J = 10.3 Hz,
= 1188.68(6) Å , Z = 4, space group P212121, dcalc = 1.874 g cm–3
,
F(000) = 648,  = 2.694 mm–1, the residual electron density
0.978/–0.298 e Å–3. The final divergence factors R1 = 0.0189 for
4200 independent reflections with I > 2(I) and wR2 = 0.0450
for all the 4368 independent reflections. Tables of the atomic

94
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Borisov et al.
coordinates, bond distances, bond and torsional angles, and paꢀ
rameters of anisotropic displacements for compound 3d were
deposited with the Cambrige Structural Database (CCDC,
12 Union Road, Cambridge CB2 1EZ, UK. Fax: +44 1223 336033;
eꢀmail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk).
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(Engl. Transl.), 2001].
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E. D. Savin, Khim. Geterotsikl. Soedin., 2005, 893 [Chem.
Heterocycl. Compd. (Engl. Transl.), 2005].
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in revised form August 8, 2011