T. Castanheiro et al. / C. R. Chimie xxx (2017) 1e10
9
2.5 equiv), and phenylboronic acid (73 mg, 0.6 mmol,
1.5 equiv). The product was isolated as a yellow oil (98 mg,
91% yield).
SCH2), 3.64 (s, 2H, SCH2), 7.13e7.26 (m, 3H, H), 7.86 (d,
J ¼ 7.2, 1H, H). 13C NMR (100.6 MHz, CDCl3)
d 0.05 (SiMe3),
13.7 (CH3), 26.3 (CH2), 28.4 (SCH2), 29.5 (SCH2), 97.9
(C^CSi), 106.2 (C^CSi), 121.2 (Cq), 125.9 (CH), 126.4
(CH), 127.7 (CH), 129.8 (CH), 136.9 (Cq), 137.2 (Cq), 138.6
(Cq).
1H NMR (400 MHz, CD2Cl2)
d
0.93 (t, J ¼ 7.5 Hz, 3H, CH3),
2.52 (q, J ¼ 7.50 Hz, 2H, CH2), 3.50 (s, 2H, SCH2), 3.59 (s, 2H,
PhSCH2), 6.53 (d, J ¼ 8.0 Hz, 1H), 6.72 (t, J ¼ 7.5 Hz, 1H), 6.86
(dd, J ¼ 7.1 Hz, 1.7 Hz, 2H), 6.93 (t, J ¼ 7.5 Hz, 1H), 6.98e7.01
(m, 4H). 13C NMR (100.6 MHz, CD2Cl2)
d
13.0 (CH3), 27.8
4.2.17. Trimethyl((2-((pent-2-yn-1-ylthio)methyl)phenyl)
ethynyl)silane (4b0)
(CH2), 28.6 (SCH2), 28.9 (SCH2),125.9 (CH),126.0 (CH),126.3
(CH), 126.4 (CH), 127.67 (2CH), 129.3 (2CH, Cq), 129.7 (CH),
138.1 (Cq), 139.9 (Cq), 140.9 (Cq), 142.8 (Cq). IR (cmꢁ1):
2963, 2928, 1478, 1451, 1441, 1372, 1192, 1054, 907, 754, 697.
HRMS (ESI, 120 eV) calculated for C18H18S [M]þ 266.1129,
found 230.1124.
The pure titled compound was isolated from the crude
mixture obtained by method C (eluent: heptane/ethyl ether
99:1) and characterized by NMR spectroscopy.
1H NMR (400 MHz, CDCl3)
d 0.26 (s, 9H, SiMe3), 1.15 (t,
J ¼ 7.5 Hz, 3H, CH3), 2.20e2.26 (m, 2H, CH2), 3.15 (s, 2H,
SCH2), 4.00 (s, 2H, SCH2Ar), 7.18 (t, J ¼ 7.7 Hz, 1H, H), 7.25e
7.34 (m, 2H, H), 7.47 (d, J ¼ 7.7, 1H, H). 13C NMR (100.6 MHz,
4.2.14. (E)-1-(1-Phenylethylidene)-1,3-dihydrobenzo[c]
thiophene (3c)
CDCl3)
d 0.08 (SiMe3), 12.7 (CH3), 14.2 (CH2), 19.6 (SCH2),
The general procedure B was followed using sulfide 1c
(96 mg, 0.4 mmol, 1 equiv), Pd(PPh3)4 (46 mg, 0.04 mmol,
34.1 (SCH2Ar), 75.1 (C^CEt), 85.2 (C^CEt), 100.1 (C^CSi),
102.8 (C^CSi), 122.9 (Cq), 126.9 (CH), 128.5 (CH), 129.0
(CH), 132.8 (CH), 140.6 (Cq).
0.1 equiv), potassium phosphate (212 mg,
1 mmol,
2.5 equiv), and phenylboronic acid (73 mg, 0.6 mmol,
1.5 equiv). The product was isolated as a yellow oil (29 mg,
30% yield).
4.2.18. (E)-(3-(Benzo[c]thiophen-1(3H)-ylidene)but-1-yn-1-yl)
trimethylsilane (4c)
1H NMR (400 MHz, C6D6)
d
2.27 (s, 3H, CH3), 3.93 (s, 2H,
SCH2), 6.66 (dd, J ¼ 6.6, 7.84 Hz, 1H), 6.76e6.82 (m, 3H),
7.06e7.15 (m, 5H). 13C NMR (100.6 MHz, CDCl3)
27.3 (CH3),
We were unable to isolate a pure sample of the titled
compound; however, it was characterized from its mixture
with compound 4c0 (obtained by method C).
d
36.0 (SCH2), 125.4 (CH), 125.9 (CH), 126.5 (Cq), 126.8 (CH),
127.3 (CH), 127.5 (CH), 129.0 (2CH), 129.6 (2CH), 137.7 (Cq),
138.9 (Cq), 143.7 (Cq), 144.5 (Cq). IR (cmꢁ1): 2922, 2850,
1688, 1593, 1489, 1471, 1454, 1440, 1264, 1026, 903, 757,
734, 698. HRMS (ESI, 120 eV) calculated for C16H14S [M]þ
238.0816, found 238.0824.
1H NMR (400 MHz, CDCl3)
d 0.26 (s, 9H, SiMe3), 2.05 (s,
3H, CH3), 4.31 (s, 2H, SCH2), 7.25e7.29 (m, 2H, H), 7.29 (dd,
J ¼ 4.6, 1.8 Hz, 1H, H), 8.78 (dd, J ¼ 4.4, 4.8 Hz, 1H, H). 13C
NMR (100.6 MHz, CDCl3)
d 0.2 (SiMe3), 24.2 (CH3), 36.5
(SCH2), 99.9 (CSiMe3), 103.7 (C]CMe), 106.9 (CCSiMe3),
124.8 (CH), 125.7 (CH), 126.8 (CH), 128.2 (CH), 138.2 (Cq),
143.2 (Cq), 149.5 (SC]C).
4.2.15. (E)-(3-(Benzo[b]thiophen-3(2H)-ylidene)pent-1-yn-1-
yl)trimethylsilane (4a)
4.2.19. Trimethyl((2-((prop-1-yn-1-ylthio)methyl)phenyl)
ethynyl)silane (4c0)
A small amount of the pure titled compound was iso-
lated from the crude mixture obtained by method A
(eluent: 100% heptane) and characterized by NMR
spectroscopy.
A small amount of the titled compound was isolated
from the crude mixture obtained by method C (eluent:
100% heptane) and characterized by NMR spectroscopy.
1H NMR (400 MHz, CDCl3)
d
0.33 (s, 9H, SiMe3), 1.25 (t,
1H NMR (400 MHz, CDCl3)
d 0.24 (s, 9H, SiMe3), 1.89 (s,
J ¼ 7.3 Hz, 3H, CH3), 2.30e2.35 (m, 3H, CH2), 4.16 (s, 2H,
3H, CH3), 4.02 (s, 2H, SCH2), 7.22 (dt, J ¼ 6.6, 1.6 Hz, 1H, H),
7.27 (dt, J ¼ 7.3, 1.8 Hz,1H, H), 7.33 (dd, J ¼ 6.8,1.8 Hz,1H, H),
7.47 (dd, J ¼ 7.3, 1.6 Hz, 1H, H). 13C NMR (100.6 MHz, CDCl3)
SCH2), 7.08e7.31 (m, 3H, H), 8.71 (d, J ¼ 8.0, 1H). 13C NMR
(100.6 MHz, CDCl3)
d 0.02 (SiMe3), 12.2 (CH3), 28.6 (CH2),
35.8 (SCH2), 102.8 (C^CSi), 105.2 (C^CSi), 117.5 (Cq), 122.4
(CH), 123.6 (CH), 125.8 (CH), 129.2 (CH), 136.3 (Cq), 144.1
(Cq), 146.0 (Cq).
d 0.1 (SiMe3), 5.3 (CH3), 39.0 (SCH2), 67.5 (SC), 91.7 (CMe),
100.3 (CSiMe3), 102.8 (CCSiMe3), 123.3 (Cq), 127.5 (CH),
128.6 (CH), 129.4 (CH), 132.7 (CH), 139.6 (Cq).
Trimethyl((2-(pent-2-yn-1-ylthio)phenyl)ethynyl)
silane (4a0). The titled compound was not isolated, as it was
obtained by method C (via Sonogashira) or A (via Stille)
only in a lesser amount, in mixture with compound 4a. One
4.2.20. Methyl (Z)-4-(benzo[b]thiophen-3-yl)hex-3-enoate
(5a00)
The general procedure D was followed starting from
sulfide 1a (102 mg, 0.4 mmol, 1 equiv). The entitled product
was isolated as a yellow oil (63 mg, 60% yield).
signal at
d
¼ 3.69 (SCH2) was assigned to this compound in
1H NMR (CDCl3).
1H NMR (400 MHz, CDCl3)
d
1.15 (t, J ¼ 8 Hz, 3H, CH3),
4.2.16. (E)-(3-(Isothiochroman-4-ylidene)pent-1-yn-1-yl)
trimethylsilane (4b)
2.51 (q, J ¼ 8 Hz, 2H, CH2), 3.37 (d, J ¼ 8 Hz, 2H, CH2), 3.78 (s,
3H, OCH3), 5.86 (t, J ¼ 8 Hz, 1H), 7.36e7.43 (m, 3H), 7.88e
We were unable to isolate a pure sample of the titled
compound; however, it was characterized from its mixture
with compound 4b0 (obtained by method A).
7.92 (m, 2H). 13C NMR (100.6 MHz, CDCl3)
d 13.3, 25.2, 33.7,
52.1,121.1122.4,122.9,123.3,124.2, 124.4, 138.6,139.1, 140.0,
140.5, 172.4. IR (cmꢁ1): 2965, 1735, 1455, 1169, 761, 735.
HRMS (ESI, 120 eV) calculated for C15H16O2S [M]þ 260.0871,
found 260.0883.
1H NMR (400 MHz, CDCl3)
d
0.10 (s, 9H, SiMe3), 1.17 (t,
J ¼ 7.5 Hz, 3H, CH3), 2.34e2.40 (m, 3H, CH2), 3.57 (s, 2H,
Please cite this article in press as: T. Castanheiro, et al., Comparative study on the reactivity of propargyl and alkynyl sulfides in