V.P. Ananikov et al. / Journal of Organometallic Chemistry 687 (2003) 451ꢀ
/461
459
4.5. Alkyne insertion reaction
4.6.4. Z-HC(SPh)Ä
/
C(SPh)ꢀ
/
CH2ꢀ
/
NMe2×
/
HOOCꢀ
/
COOH (9-C×HOOCꢀ
/
/COOH)
To each of the solutions of 3.8ꢄ
complexes 3, 4 and 5, 6 (see Section 4.3) and 8 (see
Section 4.4) in 0.5 ml of toluene the alkyne (7.6ꢄ
10ꢂ5
/
10ꢂ5 mol of
White solid. After completing the reaction and
removing the solvent and unreacted alkyne on rotor
evaporator the crude was dissolved in 3 ml of toluene.
/
mol) was added and heated with stirring at 80 8C for 2 h.
The solutions were cooled to the r.t. and the solvent was
removed on rotor evaporator. The products were
extracted with 0.5 ml of CDCl3.
The solution of HOOCꢀCOOH in 2 ml of THF (1:1 to
/
9C) was added resulting in immediate white precipitate
formation. The solid was washed with toluene, THF,
extracted with 4 ml of methanol and dried in vacuum.
1H (CD3OD; d, ppm): 7.62 (s, 1H, HCÄ
2H, Ph), 7.44ꢀ7.27 (m, 8H, Ph), 3.87 (s, 2H, ꢀ
2.83 (s, 6H, CH3ꢀ
). 13C{1H} (CD3OD; d, ppm): 166.2,
/), 7.52 (m,
/
/
CH2ꢀ),
/
4.6. General synthetic procedure
/
149.9, 134.7, 133.2, 131.9, 130.8, 130.7, 130.6, 129.4,
128.8, 118.9, 62.1, 43.1. Anal. Found: C, 58.11; H, 5.46;
N, 3.53; S, 16.16. Calc. for C19H21NO4S2: C, 58.29; H,
4.6.1. Method A*
Ar2E2 (1.0ꢄ
10ꢂ3 mol) was dissolved in 2.0 ml of
toluene followed by addition of: (i) PdCl2(PPh3)4 (21.1
mg, 3.0ꢄ
10ꢂ5 mol); (ii) PPh3 (31.5 mg, 1.2ꢄ10ꢂ4 mol
for EꢁS and 47.2 mg, 1.8ꢄ Se); (iii)
10ꢂ4 mol for Eꢁ
PhEH (5.7ꢄ
10ꢂ5 mol, diluted solution in 0.1 ml of
toluene); (iv) Et3N (9.1 mg, 9.0ꢄ
10ꢂ5 mol). The
/
using Pd(PPh3)2Cl2 as a catalyst
/
5.41; N, 3.58; S, 16.38. MS (EI), m/e 301 (Mꢃ ꢂ
/
HOOCꢀCOOH).
/
/
/
/
/
/
4.6.5. Z-HC(SPh)Ä
C(SPh)ꢀaCH2ꢀbCH2ꢀg
Light oil. 1H (CDCl3; d, ppm): 7.41 (m, 2H, Ph), 7.37
(m, 2H, Ph), 7.34ꢀ7.18 (m, 6H, Ph), 6.56 (s, 1H, HCÄ),
2.25 (t, 2H, Jꢁ CH2ꢀ), 1.48 (tt, 2H, J1ꢁ7.7
7.7 Hz, ꢀa
Hz, J2ꢁ CH2ꢀ), 1.25 (tq, 2H, J1ꢁ7.3 Hz,
7.5 Hz, ꢀb
J2ꢁ CH2ꢀ), 0.83 (t, 3H, Jꢁ CH3).
7.5 Hz, ꢀg 7.3 Hz, ꢀd
/
/
/
/
/
CH2ꢀd
CH3 (9D)
/
/
mixture was stirred upon complete dissolving of palla-
dium complex and forming homogeneous dark brown
/
/
/
/
/
/
solution. The alkyne (1.2ꢄ
reaction mixture was heated at 80 8C in a sealed tube (15
h EꢁS, 40 h EꢁSe). After completing the reaction the
/
10ꢂ3 mol) was added and
/
/
/
/
/
/
/
/
/
/
/
13C{1H} (CDCl3; d, ppm): 135.9, 134.3, 133.8, 130.5,
129.7, 129.1, 129.0, 128.9, 126.8, 126.7, 36.8, 30.7, 21.9,
13.8. Anal. Found: C, 71.99; H, 6.68; S, 21.08. Calc. for
C18H20S2: C, 71.95; H, 6.71; S, 21.34%. MS (EI), m/e
300 (Mꢃ).
product was further purified with chromatography on
silica.
4.6.2. Method B*using Pd(PPh3)4 as a catalyst
/
An earlier published [9] procedure was used except an
additional amounts of PPh3 (two and four equivalents
4.6.6. Z-HC(SPh)Ä
Light oil. 1H (CDCl3; d, ppm): 7.38 (m, 4H, Ph),
), 1.61 (q, 1H,
CH), 0.60 (d, 4H, CH2). 13C{1H} (CDCl3; d, ppm):
135.7, 134.5, 134.4, 129.8, 129.7, 129.0, 128.8, 126.9,
126.4, 18.3, 6.6. Anal. Found: C, 71.95; H, 5.72; S,
22.42. Calc. for C17H16S2: C, 71.78; H, 5.67; S, 22.55.
MS (EI), m/e 284 (Mꢃ).
/
C(SPh)ꢀ
/
C3H5 (9E)
for Eꢁ
/
S and EꢁSe, respectively) were added and the
/
7.32ꢀ
/
7.16 (m, 6H, Ph), 6.62 (s, 1H, HCÄ
/
reaction was performed in a sealed tube. The reaction
was performed with 3 mol% of palladium catalyst and
alkyne:Ar2E2ꢁ1.2:1 ratio.
/
Compounds 10B, 9B [9] and 10C [10] were identified
according to published data. Structure elucidation for
the other compounds was made utilizing two-dimen-
sional NOESY, LR-COSY, 1H-13C HSQC, 1H-13C
4.6.7. Z-HC(SePh)Ä
Light oil. 1H (CDCl3; d, ppm): 7.54 (m, 4H, Ph), 7.27
), 1.60 (m, 1H, CH),
/
C(SePh)ꢀ
/
C3H5 (10E)
HMBC experiments. For the selenium-containing pro-
ducts two-dimensional Hꢀ77
1
/
Se HMQC NMR experi-
(m, 6H, Ph), 6.97 (br s, 1H, HCÄ
/
ment was performed. Compound 16 (Scheme 4) was
obtained as unseparable 16:17 mixture and identified
with the above set of NMR experiments.
0.58 (m, 4H, CH2). 13C{1H} (CDCl3; d, ppm): 137.2,
132.6, 132.4, 131.2, 129.9, 129.2, 129.1, 127.4, 127.2,
127.1, 20.5, 7.2. Anal. Found: C, 54.02; H, 4.29; Se,
41.89. Calc. for C17H16Se2: C, 53.98; H, 4.26; S, 41.75%.
MS (EI), m/e 380 (Mꢃ).
4.6.3. Z-HC(SPh)Ä
/
C(SPh)ꢀ
Yellow oil. H (CDCl3; d, ppm): 7.39 (m, 2H, Ph),
7.34 (s, 1H, HCÄ), 7.33ꢀ7.21 (m, 7H, Ph), 7.13 (m, 1H,
Ph), 1.80ꢀ
1.50 (m, 9H, CH2), 1.64 (m, 1H, 1/2CH2).
/
C6H10(OH) (9A)
1
/
/
4.6.8. Z-(p-MePhSe)HCÄ
CH2OH (14B)
Yellow oil, solidified on cooling. 1H (CDCl3; d, ppm):
7.44 (m, 4H, Ar), 7.10 (m, 4H, Ar), 6.99 (s, 1H, HCꢁ),
6.0
/
C(p-MePhSe)ꢀ
/
CH2ꢀ
/
/
13C{1H} (CDCl3; d, ppm): 138.2, 135.5, 135.1, 130.5,
129.1, 128.9, 127.3, 126.8, 125.4, 75.8, 36.3, 25.2, 21.8.
Anal. Found: C, 70.20; H, 6.76; S, 18.53. Calc. for
C20H22OS2: C, 70.13; H, 6.47; S, 18.72%. MS (EI), m/e
342 (Mꢃ).
/
3.66 (t, 2H, Jꢁ
/
6.2 Hz, CH2OH), 2.47 (t, 2H, Jꢁ
/
Hz, CH2), 2.33 (s, 3H, CH3), 2.32 (s, 3H, CH3). 13C{1H}
(CDCl3; d, ppm): 137.7, 137.6, 133.4, 133.1, 131.1,