β-Aminoselenenation of alkenes with arylselenenamides in the presence of sulfamic acid

Full text of DOI:10.1007/s11172-011-0034-x

Russian Chemical Bulletin, International Edition, Vol. 60, No. 1, pp. 198—199, January, 2011
198
βꢀAminoselenenation of alkenes with arylselenenamides
in the presence of sulfamic acid
A. N. Chernysheva, R. L. Antipin, A. A. Borisenko, E. K. Beloglazkina, and N. V. Zyk
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: (495) 939 0290. Eꢀmail: a.n.chernysheva@gmail.com
In the present study, we suggested a new method of the
for the protons HCSe and HCN is ∼25 Hz, which unamꢀ
synthesis of βꢀaminoalkyl aryl selenides by the reaction of
electrophilic selenenation of alkenes with phenylselenꢀ
enamide 1 in the presence of HOSO2NH2.
We have shown earlier that the reaction of arylselenenꢀ
amides with unsaturated compounds in the presence of
phosphorus(V) or sulfur(IV) oxohalides results in the corꢀ
responding βꢀhalogenalkyl aryl selenides in high yields.1,2
Also, the possibility of a reaction of arylsulfenamides with
olefins in the presence of sulfamic acid resulting in substiꢀ
tuted aminoalkyl aryl sulfides was found.3
It is of note that the Gabriel reaction of nucleophilic
substitution of the amino group for halogen successfully
used for the preparation of βꢀaminoalkyl sulfides4 is inapꢀ
plicable in the case of seleniumꢀcontaining analogs. The
other known method for obtaining βꢀaminoalkyl aryl seꢀ
lenides (in the form of NBoc derivatives)5 with olefins as
the starting compounds requires preliminary aziridination
of the alkenes, the use of indium iodide, and the inert
atmosphere.
biguously indicated transꢀdiequatorial orientation of the
substituents and the axial positions of the corresponding
protons of the cyclohexane moiety. In the twoꢀdimenꢀ
sional correlation spectrum 13C—1H HMBC of compound
3, intense crossꢀpeaks corresponding to the C(1´)—Ha(1)
and C(1´)—Hb(1) (3J) couplings are present. Besides, in
the 13C NMR spectrum of amino selenide 3 satellite peaks
were observed corresponding to the 77Se and 13C coupling
with J = 65 Hz.
Thus, we suggested a convenient method for the synꢀ
thesis of primary alkylamines containing arylseleno group
in the βꢀposition.
1
H and 13C NMR spectra were recorded on a Varian VXRꢀ400
instrument in CDCl3 at 400.13 and 100.61 MHz, respectively.
IR spectra were obtained on a URꢀ20 instrument for suspensions
in Nujol. Elemental analysis was performed on an Elementar
Variocube CHNꢀanalyzer. Diethyl phenylselenenamide (1) was
synthesized from diphenyl diselenide according to the known
procedure.2
Addition of phenylselenenamide to alkenes (general procedure).
To a boiling suspension of sulfamic acid (11 mmol) in dry nitroꢀ
methane (5 mL), a solution of an alkene (6.6 mmol) and phenylꢀ
selenenamide 1 (2.2 mmol) in MeNO2 (10 mL) was added, the
reaction mixture was refluxed to complete disappearance of the
starting selenenamide (TLC monitoring). Then the solution was
filtered and the solvent was evaporated. The obtained yellow oil
was dissolved in 5% HCl (20 mL) and refluxed for 4 h. Activated
carbon was added and the mixture was refluxed for 30 min. The
We used cyclohexene and hexꢀ1ꢀene in our experiꢀ
ments. The reaction of phenylselenenamide 1 (see Ref. 3)
with hexꢀ1ꢀene occurs regioselectively with the formation
of 2ꢀaminoꢀ1ꢀphenylselenohexane (2). transꢀAmino seꢀ
lenide 3 was obtained from cyclohexene (Scheme 1).
The structures of the obtained products were estabꢀ
lished by 1H and 13C NMR spectroscopy. In the 1H NMR
spectrum of amino selenide 2, a halfꢀwidth of the signals
Scheme 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 189—190, January, 2011.
1066ꢀ5285/11/6001ꢀ198 © 2011 Springer Science+Business Media, Inc.

2ꢀAminoalkyl selenides
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
199
hot solution was filtered, a solution of NaOH was added to pH ≥ 9,
the mixture was extracted with diethyl ether (2×25 mL). After
removal of the solvent in vacuo, compounds 2 and 3 were obꢀ
tained in a form of amberꢀcolored oils.
ences (Program "Theoretical and Experimental Study of
the Nature of Chemical Bond and Mechanisms of Chemꢀ
ical Reactions and Processes").
2ꢀAminoꢀ1ꢀphenylselenohexane (2). Yield 0.06 g (20%). IR,
ν/cm–1: 3375, 3360 (NH2). 1H NMR, δ: 0.89 (t, 3 H, Me,
J = 7.3 Hz); 1.32 (m, 4 H, CH2); 1.50 (2 H, HC(3)); 1.63 (br.s,
2 H, NH2); 2.78 (dd, 1 H, HCSe, J1 = 8.5 Hz, J2 = 12.4 Hz);
2.89 (m, 1 H, HCN); 3.12 (dd, 1 H, НCSe, J1 = 5.2 Hz,
J2 = 12.4 Hz); 7.26 (m, 3 H, Ph); 7.54 (m, 2 H, Ph). 13С NMR,
δ: 14.0, 22.7, 28.5, 37.3, 37.8 (CSe), 50.9 (CN), 126.9, 129.0,
132.8, 135.3.
transꢀ2ꢀAminoꢀ1ꢀphenylselenocyclohexane (3). Yield 0.37 g
(65%). Found (%): C, 56.62; H, 6.60; N, 5.50. С12H17NSe. Calꢀ
culated (%): C, 56.69; H, 6.74; N, 5.51. IR, ν/cm–1: 3380, 3360
(NH2). 1H NMR, δ: 1.20 (m, 3 H, HC(5), HC(4)); 1.47 (m, 1 H,
HC(4)); 1.67 (m, 2 H, HC(6), HC(3)); 1.84 (br.s, 2 H, NH2);
2.00 (d, 1 H, HC(6), J1 = 13.0); 2.15 (dt, 1 H, HC(3), J1 = 4.0 Hz,
J2 = 13.0 Hz); 2.60 (ddd, 1 H, HCSe, J1 = 4.0 Hz, J2 = 10.1 Hz,
J3 = 12.0 Hz); 2.81 (dt, 1 H, HCN, J1 = 4.0 Hz, J2 = 10.1 Hz);
7.25 (m, 3 H, Ph); 7.58 (m, 2 H, Ph). 13C NMR, δ: 25.1, 27.2,
34.3, 33.8, 54.3 (CSe), 54.4 (CN), 127.7, 127.9, 128.9, 135.8.
References
1. N. V. Zyk, E. K. Beloglazkina, R. L. Antipin, Izv. Akad.
Nauk, Ser. Khim., 2004, 2250 [Russ. Chem. Bull., Int. Ed.,
2004, 53, 2352].
2. R. L. Antipin, V. N. Klak, E. K. Beloglazkina, N. V. Zyk,
Zh. Org. Khim., 2009, 45, 857 [Russ. J. Org. Chem. (Engl. Transl.),
2009, 45, 842].
3. N. S. Zefirov, N. V. Zyk, A. G. Kutateladze, E. K. Butina,
Zh. Org. Khim., 1990, 26, 671 [J. Org. Chem. USSR
(Engl. Transl.), 1990, 26].
4. E. K. Beloglazkina, N. S. Dubinina, A. A. Moiseeva, N. V.
Zyk, Vestn. MGU, Ser. 2. Khim., 2007, 48, 193 [Vestn. Mosk.
Univ., Ser. 2: Khim. (Engl. Transl.), 2007, 48, No. 3].
5. A. L. Braga, P. H. Schneider, M. W. Paixao, A. M. Deobald,
C. Peppe, D. P. Bottega, J. Org. Chem., 2006, 71, 4305.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ
00707a) and Presidium of the Russian Academy of Sciꢀ
Received June 24, 2010;
in revised form October 25, 2010