Nanosaltꢀcatalyzed thiol addition to alkynes
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
53
version of alkynes (the temperature and the reaction time are
given in Table 5), and the extent of the reaction was monitored
by the Н NMR data. After the end of the reaction, residues of
unreacted alkyne were removed on a rotary evaporator under
reduced pressure and the product was purified by flash chromatoꢀ
graphy on silica gel.
(m, 2 H); 2.16 (s, 6 H, 2 CH3); 2.14—2.27 (m, 2 H, CH2); 3.01
(s, 2 H, CH2); 2.98—3.11 (m, 1 H); 5.64 (t, 1 H, CH, J = 7.4 Hz).
13C NMR (acetoneꢀd6), : 14.48, 22.90, 26.64, 26.70, 34.01,
43.59, 45.33, 60.67, 131.86, 134.74. MS (ESI), m/z: 228.1784
[M + H]+. C13H25NSH. Calculated: 228.1780.
1
Eꢀ3ꢀ(Cyclohexylthio)ꢀ1ꢀdimethylaminoꢀ2ꢀpentene (3a).
1Н NMR (acetoneꢀd6), : 1.05 (t, 1 H, CH3, J = 7.5 Hz); 1.23—1.41
(m, 5 H); 1.57—1.64 (m, 1 H); 1.70—1.79 (m, 2 H); 1.90—2.00
(m, 2 H); 2.15 (s, 6 H, 2 CH3); 2.23 (q, 2 H, CH2, J = 7.5 Hz);
2.92 (d, 2 H, CH2, J = 6.9 Hz); 2.94—3.01 (m, 1 H); 5.46 (t, 1 H,
CH, J = 6.9 Hz). 13C NMR (acetoneꢀd6), : 13.87, 26.07, 26.54,
26.61, 33.92, 43.28, 45.46, 57.77, 126.32, 139.08. MS (ESI),
m/z: 228.1786 [M + H]+. C13H25NSH. Calculated: 228.1780.
Eꢀ1,2ꢀDiphenylvinyl(cyclohexyl) sulfide (2b). 1Н NMR (acetꢀ
oneꢀd6), : 1.09—1.27 (m, 3 H); 1.31—1.41 (m, 2 H); 1.47—1.55
(m, 1 H); 1.64—1.73 (m, 2 H); 1.84—1.95 (m, 2 H); 2.66—2.74
(m, 1 H); 6.88 (s, 1 H); 6.91—6.98 (m, 2 H); 7.01—7.09 (m, 3 H);
7.27—7.36 (m, 5 H). 13C NMR (acetoneꢀd6), : 26.37, 33.76,
44.00, 127.42, 128.77, 128.82, 129.40, 129.70, 130.33, 132.27,
133.78, 137.72, 138.50, 139.59. MS (ESI), m/z: 295.1509 [M + H]+.
C20H22SH. Calculated: 295.1515.
Eꢀ2ꢀ(Cyclohexylthio)ꢀ2ꢀpentenꢀ1ꢀol (2c). 1Н NMR (acetꢀ
oneꢀd6), : 0.98 (t, 3 H, J = 7.6 Hz); 1.20—1.37 (m, 5 H); 1.56—1.62
(m, 1 H); 1.70—1.77 (m, 2 H); 1.91—1.98 (m, 2 H); 2.17—2.23
(m, 2 H); 2.97—3.03 (m, 1 H); 3.61 (t, 1 H, J = 5.3 Hz); 4.18
(d, 2 H, J = 5.3 Hz); 5.75 (t, 1 H, J = 7.5 Hz). 13C NMR
(acetoneꢀd6), : 14.58, 22.71, 26.58, 26.60, 34.04, 44.09, 61.29,
134.04, 137.67. MS (ESI), m/z: 201.1303 [M + H]+. C11H20OSH.
Calculated: 201.1308.
Eꢀ3ꢀ(Cyclohexylthio)ꢀ2ꢀpentenꢀ1ꢀol (3c). 1Н NMR (acetꢀ
oneꢀd6), : 1.06 (t, 3 H, J = 7.5 Hz); 1.22—1.41 (m, 5 H); 1.56—1.64
(m, 1 H); 1.71—1.77 (m, 2 H); 1.94—2.01 (m, 2 H); 2.22 (q, 2 H,
J = 7.5 Hz); 2.89—3.02 (m, 1 H); 3.59 (br.s, 1 H); 4.13 (d, 2 H,
J = 6.4 Hz); 5.57 (t, 1 H, J = 6.4 Hz). 13C NMR (acetoneꢀd6),
: 14.29, 26.11, 26.57, 26.59, 33.84, 43.27, 59.04, 127.61, 130.87.
MS (ESI), m/z: 223.1117 [M + Na]+. C11H20OSNa. Calculated:
223.1127.
Eꢀ2ꢀ(Cyclohexylthio)ꢀ3ꢀphenylꢀ2ꢀpropenꢀ1ꢀol (2d). 1Н NMR
(acetoneꢀd6), : 1.23—1.34 (m, 1 H); 1.34—1,45 (m, 4 H);
1.59—1.66 (m, 1 H); 1.73—1.81 (m, 2 H); 2.01—2.08 (m, 2 H);
3.19—3.28 (m, 1 H); 4.06 (t, 1 H, J = 5.4 Hz); 4.31 (d, 2 H,
J = 5.4 Hz); 6.71 (s, 1 H); 7.24 (t, 1 H, J = 7.3 Hz); 7.34 (t, 2 H,
J = 7.6 Hz); 7.37—7.42 (m, 2 H). 13C NMR (acetoneꢀd6),
: 26.60, 34.04, 44.16, 61.86, 127.71, 129.08, 129.47, 130.78,
137.80, 138.96. MS (ESI), m/z: 271.1127 [M + Na]+. C15H20OSNa.
Calculated: 271.1127.
Preparation of catalyst samples for FEꢀSEM study (general
procedure). The reaction mixture was centrifuged (4000 rpm,
5 min), and the isolated precipitate was washed 4 times with
CH2Cl2 and dried in vacuo. The samples were obtained from the
reaction mixture in 20 min (see Fig. 1, a, b) and 1 h (see Fig. 1, c
and d) after the start of the reaction. When beforehand preꢀ
pared [Pd(SCy)2]n was used, the samples were isolated before
the reaction (see Fig. 2, a) and 2 h after the start of the reaction
(see Fig. 2, b).
The samples for the analysis were prepared using the magneꢀ
tron sputtering method recently described.25 The microstructure
of the samples was studied by field emission scanning electron
microscopy (FEꢀSEM) on a Hitachi SU8000 electron microꢀ
scope. Images were recorded in the regime of secondary elecꢀ
tron detection at a accelerating voltage of 10 kV and a working
distance of 8—10 mm. The morphology of the samples was studꢀ
ied using a correction for surface sputtering effects of the conꢀ
ducting layer.
Molecular structure of product 2b. Colorless plateꢀlike crysꢀ
tals С20H22S (2b) (M = 292.42), monoclinic, at 100 К a =
= 9.3815(5) Å, b = 11.614(1) Å, c = 10.1921(6) Å, = 111.319(1),
V = 1569.0(2) Å3, space group P/21c, Z = 4, dcalc = 1.238 g cm–3
.
An experimental set of 14 582 reflections was obtained on a Bruker
APEX II CCD area detector diffractometer at 100 К (ꢀМоК
radiation, 2max = 54.0) from a single crystal 0.60×0.45×0.23 mm
in size. After averaging equivalent reflections, 3415 independent
reflections (Rint = 0.0224) were obtained, which were used for
structure determination and refinement. No absorption correcꢀ
tion ( = 0.197 mm–1) was applied, and the transmission coeffiꢀ
cients Tmax and Tmin determined using the SADABS program
(Bruker, Programs APEX II, version 2.0ꢀ1; SAINT, version
7.23A), SADABS, version 2004/1; XPREP, version 2005/2;
SHELXTL, version 6.1. Bruker AXS Inc., Madison, WI, USA,
2005) are 0.956 and 0.891, respectively. The structure was solved
by a direct method. All nonꢀhydrogen atoms were localized in
difference electron density syntheses and refined by F2 in the
hkl
anisotropic approximation; all hydrogen atoms were placed in
geometrically calculated positions and took into account in reꢀ
finement in the riding model with U(H) = 1.2 U(C), where U(C)
is the equivalent temperature factor of the carbon atom to which
the corresponding H atom is bound. The final value of reliability
factors are R1 = 0.0328 (calculated from Fhkl for 2990 reflections
with I > 2(I)), wR2 = 0.0839 (calculated from F2hkl for all 3415
reflections), goodnessꢀofꢀfit is 1.019, 190 refined parameters.
All calculations were performed using the SHELXTL program
package. The coordinates of atoms, bond lengths and bond anꢀ
gles, and temperature parameters were deposited with the Camꢀ
bridge Crystallographic Data Centre (CCDC 918936).
Eꢀ3ꢀ(Cyclohexylthio)ꢀ3ꢀphenylꢀ2ꢀpropenꢀ1ꢀol (3d). 1Н NMR
(acetoneꢀd6), : 1.15—1.34 (m, 5 H); 1.49—1.56 (m, 1 H);
1.64—1.72 (m, 2 H); 1.82—1.90 (m, 2 H); 2.61—2.68 (m, 1 H);
3.72 (br.s, 1 H); 4.01 (d, 2 H, J = 6.8 Hz); 6.08 (t, 1 H, J = 6.8 Hz);
7.29—7.43 (m, 5 H). 13C NMR (acetoneꢀd6), : 26.37, 26.44,
33.70, 43.96, 60.24, 128.76, 128.91, 129.95, 131.77, 137.51, 139.01.
EꢀEthylꢀ2ꢀ(cyclohexylthio)ꢀ3ꢀphenyl acrylate (2e). 1Н NMR
(acetoneꢀd6), : 1.18 (t, 3 H, J = 7.0 Hz); 1.24—1.42 (m, 5 H);
1.57—1.64 (m, 1 H); 1.72—1.81 (m, 2 H); 1.97—2.07 (m, 2 H);
3.03—3.10 (m, 1 H); 4.21 (q, 2 H, J = 7.1 Hz); 7.00 (s, 1 H);
7.26—7.39 (m, 5 H, Ar). 13C NMR (acetoneꢀd6), : 14.22, 26.36,
26.46, 33.87, 45.73, 61.93, 128.84, 129.20, 129.30, 131.76,
133.59, 136.49, 168.11.
Characteristics of Isolated Compounds
Eꢀ2ꢀ(Cyclohexylthio)ꢀ1ꢀdimethylaminoꢀ2ꢀpentene (2a).
1Н NMR (acetoneꢀd6), : 0.96 (t, 3 H, CH3, J = 7.5 Hz); 1.16—1.44
(m, 5 H); 1.55—1.67 (m, 1 H); 1.68—1.81 (m, 2 H); 1.89—2.00
EꢀEthylꢀ3ꢀ(cyclohexylthio)ꢀ3ꢀphenyl acrylate (3e). 1Н NMR
(acetoneꢀd6), : 1.01 (t, 3 H, J = 7.1 Hz); 1.26—1.48 (m, 5 H);