Organometallics
Article
(d, J = 8.3 Hz, 0.75H), 9.08 (d, J = 8.2 Hz, 0.25H), 7.71 (d, J = 7.9
Hz, 1H), 7.67 (t, J = 8.0 Hz, 1H), 7.44 (t, J = 7.5 Hz, 1H), 5.99 (td, J
= 16.9, 6.9 Hz, 1H), 5.40−5.11 (m, 2H), 3.50−3.38 (m, 2H), 2.86−
2.70 (m, 2H). 13C NMR (151 MHz, CDCl3): δ 174.35, 173.72,
150.39, 134.93, 134.86, 131.22, 131.11, 127.78, 125.72, 122.72,
122.62, 121.35, 121.26, 118.23, 118.06, 35.50, 35.45, 33.08, 32.96,
samarium(II) iodide (SmI2) (0.5 mmol, 0.1 M solution in THF, 1
equiv). To this mixture was added 1,2-DCE (5 mL, 0.1 M), and the
vial was capped. The reaction mixture was stirred at 500 rpm at 45 °C
for 12 h. Without cooling to room temperature, the crude solution
was transferred into a new 1 dram (4 mL) vial. This uncapped vial
with the crude mixture was placed inside a scintillation vial (20 mL).
Diethyl ether (2 mL) was placed the scintillation vial without any
addition into the 1 dram vial containing the crude material. The
scintillation vial was capped and allowed to sit undisturbed for 72 h.
The 1 dram vial was then removed from the scintillation vial and the
solvent carefully removed with a pipet, leaving crystals, which were
washed with additional diethyl ether (3 × 3 mL). The remaining
diethyl ether was then removed in vacuo to provide the pure product.
While some X-ray-quality crystals were retrievable, the yield of crystals
was low (<10%). The reaction was rerun following a literature
procedure.21
+
29.86. HRMS: calcd for C22H2479BrN2106PdS4 [M − Br + 2H]+,
628.9041; found, 628.9022. Single crystals suitable for X-ray
diffraction were obtained directly from the procedure described
Complex 3b. The title compound was prepared with 2-(but-3-en-
1-ylthio)benzo[d]thiazole (1a) and PdCl2. Crystals were regrown to
X-ray quality by slow evaporation of CDCl3 in an NMR tube.
1
Purification afforded 3b as a yellow crystal (32 mg, 51%). H NMR
(600 MHz, CDCl3): δ 9.26 (dt, J = 8.3, 0.9 Hz, 0.65H), 9.18 (dt, J =
8.2, 0.9 Hz, 0.35H), 7.76−7.71 (m, 1H), 7.68 (ddd, J = 8.4, 7.3, 1.2
Hz, 1H), 7.45 (dddd, J = 8.2, 7.2, 6.1, 1.1 Hz, 1H), 6.04−5.93 (m,
1H), 5.36−5.18 (m, 2H), 3.48−3.42 (m, 2H), 2.82−2.71 (m, 2H).
13C NMR (151 MHz, CDCl3): δ 173.90, 173.27, 166.39, 152.87,
149.53, 135.26, 134.77, 134.33, 134.25, 130.67, 130.56, 127.32,
125.57, 125.16, 125.13, 123.73, 121.85, 121.70, 121.05, 120.77,
120.69, 120.50, 117.65, 117.48, 116.51, 34.82, 34.80, 32.90, 32.42,
1H NMR (600 MHz, DMSO-d6): δ 8.32 (dt, J = 8.3, 2.0 Hz, 1H),
8.11 (dd, J = 8.6, 3.0 Hz, 1H), 7.86−7.78 (m, 1H), 7.71 (td, J = 7.7,
3.0 Hz, 1H), 5.54 (dh, J = 9.6, 3.1 Hz, 1H), 3.74−3.66 (m, 2H),
3.67−3.54 (m, 2H), 3.01 (dq, J = 15.1, 3.3 Hz, 1H), 2.46 (ddd, J =
15.5, 10.0, 4.3 Hz, 1H). 13C NMR (151 MHz, DMSO): δ 175.83,
140.77, 128.69, 127.66, 127.09, 123.98, 114.96, 55.10, 23.25, 23.16,
2.10. Single crystals suitable for X-ray diffraction were obtained
directly from the procedure described above (CCDC 2057863).28
Synthetic Procedure for [1,1′-Biphenyl]-4-carbaldehyde
(7).25 In a 1 dram (4 mL) vial equipped with a magnetic stir bar
were placed 4-bromobenzaldehyde (0.3 mmol, 1 equiv), phenyl-
boronic acid (0.36 mmol, 1.2 equiv), potassium carbonate (K2CO3)
(1.0 mmol, 2 equiv), and ( )-2a (0.0015 mmol, 0.5 mol %). To this
mixture was added a 1/1 mixture of H2O and DMF (3 mL, 0.1 M).
The vial was capped, placed on a preheated hot plate at 100 °C, and
stirred at 500 rpm for 12 h. The reaction mixture was removed from
the stir plate and cooled. The contents of the vial were transferred to a
separation vial with subsequent washing of H2O and EtOAc.
Additional H2O (50 mL) was placed in the separation vial, and the
desired material was extracted with EtOAc (3 × 50 mL) and dried
with Na2SO4. After the solvent was removed in vacuo, the crude
residue was purified by SiO2 gel column chromatography (5%
EtOAc/95% hexanes). Purification afforded 7 as a white solid (90 mg,
>95%).
+
32.30, 29.27. HRMS: calcd for C22H2235ClN2106PdS4 [M − Cl]+,
582.9386; found, 582.9402. Single crystals suitable for X-ray
diffraction were obtained directly from the procedure described
Complex 4. The title compound was prepared with 2-((2-
methylbutyl)thio)benzo[d]thiazole (1e) and Pd(TFA)2. Purification
1
afforded 4 as an orange crystal (23 mg, 40%). H NMR (600 MHz,
CDCl3): δ 9.30 (dd, J = 11.2, 8.4 Hz, 1H), 7.70 (dq, J = 12.6, 8.8 Hz,
2H), 7.44 (t, J = 7.7 Hz, 1H), 3.37 (ddd, J = 13.1, 7.8, 5.9 Hz, 1H),
3.25−3.16 (m, 1H), 2.00 (qd, J = 13.7, 6.7 Hz, 1H), 1.68 (dtt, J =
13.0, 10.1, 6.3 Hz, 1H), 1.44 (dpd, J = 14.8, 7.4, 3.0 Hz, 1H), 1.19
(dd, J = 6.7, 4.2 Hz, 3H), 1.01 (q, J = 7.1 Hz, 3H). 13C NMR (151
MHz, CDCl3): δ 176.59, 176.41, 149.81, 149.72, 130.54, 130.42,
128.08, 127.98, 125.81, 125.78, 122.02, 122.00, 121.18, 43.14, 43.04,
35.07, 35.01, 28.98, 28.94, 19.01, 11.37. HRMS: calcd for
+
C26H30F3N2O2106PdS4 [M − TFA]+, 693.0177; found, 693.0168.
Single crystals suitable for X-ray diffraction were obtained directly
from the procedure described above (CCDC 2057871).28
1H NMR (600 MHz, CDCl3): δ 10.06 (s, 1H), 7.95 (d, J = 8.2 Hz,
2H), 7.75 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.8
Hz, 2H), 7.42 (t, J = 7.5 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ
192.00, 147.24, 139.76, 135.27, 130.35, 129.10, 128.56, 127.75,
127.44.
Synthetic Procedure for Complex 5. In a 1 dram (4 mL) vial
equipped with a magnetic stir bar were placed 2-(but-3-en-1-
ylthio)benzo[d]thiazole (1a) (0.10 mmol, 2 equiv) and silver triflate
(AgOTf) (0.05 mmol, 1 equiv). To this mixture was added 1,2-DCE
(0.5 mL, 0.1 M), and the vial was capped. The reaction mixture was
stirred at 500 rpm at 45 °C for 12 h. Without cooling to room
temperature, the crude solution was transferred into a new 1 dram (4
mL) vial. This uncapped vial with the crude mixture was placed inside
a scintillation vial (20 mL). Diethyl ether (2 mL) was placed in the
scintillation vial without any addition into the 1 dram vial containing
the crude material in preparation for vapor diffusion. The scintillation
vial was capped and allowed to sit undisturbed for 72 h. The 1 dram
vial was then removed from the scintillation vial and the solvent
carefully removed with a pipet, leaving crystals, which were washed
with additional diethyl ether (3 × 3 mL). The remaining diethyl ether
was then removed in vacuo to provide the pure product 5 as a gray
crystal (20 mg, 42%).
Synthetic Procedure for (E)-4-(4-Methylstyryl)-
benzaldehyde (8).26 In a 1 dram (4 mL) vial equipped with a
magnetic stir bar were placed the corresponding 4-bromobenzalde-
hyde (0.3 mmol, 1 equiv), 1-methyl-4-vinylbenzene (0.36 mmol, 1.2
equiv), potassium carbonate (K2CO3) (1.0 mmol, 2 equiv), and
( )-2a (0.0015 mmol, 0.5 mol %). To this mixture was added a 1/1
mixture of H2O and DMF (3 mL, 0.1 M). The vial was capped, placed
on a preheated hot plate at 100 °C, and stirred at 500 rpm for 12 h.
The reaction mixture was removed from the stir plate and cooled. The
contents of the vial were transferred to a separation vial with
subsequent washing of H2O and EtOAc. Additional H2O (50 mL)
was placed in the separation vial, and the desired material was
extracted with EtOAc (3 × 50 mL) and dried with Na2SO4. After the
solvent was removed in vacuo, the crude residue was purified by SiO2
gel column chromatography (5% EtOAc/95% hexanes). Purification
afforded 8 as a yellow solid (45 mg, 67%).
1H NMR (600 MHz, acetone-d6): δ 8.12 (dd, J = 15.3, 8.2 Hz,
2H), 7.59 (ddd, J = 8.3, 5.0, 1.3 Hz, 1H), 7.56−7.49 (m, 1H), 6.24
(ddtd, J = 13.4, 8.4, 6.7, 1.8 Hz, 1H), 5.45−5.36 (m, 2H), 3.71 (td, J
= 6.5, 1.8 Hz, 2H), 2.75 (q, J = 6.7 Hz, 2H). 13C NMR (151 MHz,
acetone-d6): δ 171.79, 152.45, 135.76, 134.98, 128.28, 126.71, 122.93,
1H NMR (600 MHz, CDCl3): δ 9.99 (s, 1H), 7.86 (d, J = 8.0 Hz,
2H), 7.64 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 7.8 Hz, 2H), 7.27−7.19
(m, 3H), 7.10 (d, J = 16.2 Hz, 1H), 2.38 (s, 3H). 13C NMR (151
MHz, CDCl3): δ 191.79, 143.83, 138.77, 135.31, 133.93, 132.33,
130.40, 129.71, 126.99, 126.92, 126.47, 21.49.
+
122.63, 114.01, 36.68, 33.85. HRMS: calcd for C11H11107AgNS2 [M
− OTf]+, 327.9384; found, 327.9395. Single crystals suitable for X-ray
diffraction were obtained directly from the procedure described above
Synthetic Procedure for 5-(Benzo[d]oxazol-2-yl)thiophene-
2-carbaldehyde (9).27 In a 1 dram (4 mL) vial equipped with a
magnetic stir bar were placed benzo[d]oxazole (0.1 mmol, 1 equiv),
thiophene-2-carbaldehyde (0.2 mmol, 2 equiv), silver acetate
Synthetic Procedure for 4-(Iodomethyl)-3,4-dihydro-2H-
benzo[4,5]thiazolo[2,3-b][1,3]thiazin-5-ium Triiodide (6). In a
1 dram (4 mL) vial equipped with a magnetic stir bar were placed 2-
(but-3-en-1-ylthio)benzo[d]thiazole (1a) (0.5 mmol, 1 equiv) and
F
Organometallics XXXX, XXX, XXX−XXX