The Journal of Organic Chemistry
Note
4
7
Isolation of 1,3-Bis(2,6-diisopropylphenyl)-2,4-diphenyl-
Anthracene (10a). Obtained as a white solid. 8.7 mg. Yield 98%.
1
1
H-imidazol-3-ium Iodide (4) through Hydrodehalogenation
H NMR (500 MHz, CDCl ): δ 8.43 (s, 2H), 8.02−8.00 (m, 4H),
.48−7.46 (m, 4H) ppm; C { H} NMR (125 MHz, CDCl ): δ
31.7, 128.2, 126.2, 125.3 ppm.
General Procedure for Catalytic Hydrosilylation of Alkene.
In a 15 mL J. Young pressure tube, 1.5 mg (0.0025 mmol) of
Ni(PLY) (THF) ] was taken and dried under vacuum for 1 h. It was
transferred to a glovebox to add 4.1 mg (0.0075 mmol) of 2, followed
by the addition of 1 mL of THF. The color of the solution
immediately turned into dark green. It was stirred for 10 min at room
temperature inside the glovebox. Next, Ph SiH (186 μL, 1.0 mmol)
and 1-octene (157 μL, 1.0 mmol) were added to it. It was capped
properly and stirred at room temperature for 2 h. On completion, the
reaction mixture was directly loaded to a column after dilution with
hexane. Octyldiphenylsilane was isolated through silica (100−200
mesh) using hexane as an eluent, and it was characterized using H,
C NMR spectroscopy and matched with the literature values.
colorless liquid was obtained (284 mg, yield 96%). H NMR (400
MHz, CDCl ) δ 7.62−7.60 (m, 4H), 7.44−7.38 (m, 6H), 4.91 (t, J =
.6 Hz, 1H), 1.54−1.48 (m, 2H), 1.43−1.40 (m, 2H), 1.32−1.29 (m,
3
13
Process. Inside an argon filled glovebox, a 25 mL Schlenk flask was
charged with a magnetic bar, 54.2 mg (0.10 mmol) of 2 and dissolved
in 2 mL of diethyl ether. 31.1 mg (0.10 mmol) of 1-(benzyloxy)-4-
iodobenzene in ether (2 mL) was added to it; the color of the solution
immediately turned into reddish yellow from dark green with
instantaneous formation of a white precipitate. The Schlenk flask
was capped properly and taken outside the glovebox to stir it at room
temperature for 12 h. On completion, the reaction mixture was
washed with ether (10 mL × 4), and the white precipitate was
collected (19.8 mg, yield 30%). Colorless single crystals of 4 suitable
for single crystal diffraction study were grown from a saturated THF
solution at 25 °C under an argon atmosphere within 12 h. Compound
1
7
1
3
[
2
2
2
2
1
13
4
was characterized by H, C NMR spectroscopic studies as well as
1
by single crystal X-ray diffraction study. H NMR (400 MHz, CDCl )
3
δ 8.85 (s, 1H), 7.64 (t, J = 8.0 Hz, 1H), 7.58 (t, J = 8.0 Hz, 1H),
1
7
.43−7.37 (m, 6H), 7.34−7.31 (m, 4H), 7.23 (t, J = 8.0, 2H), 6.94 (d,
13
39
A
J = 8.0, 2H), 2.57−2.52 (m, 2H), 2.48−2.42 (m, 2H), 1.39 (d, J = 6.8
1
1
3
Hz, 6H), 1.01 (d, J = 7.2 Hz, 6H), 0.87−0.85 (m, 12H) ppm.
C
1
{
1
1
H} NMR (100 MHz, CDCl ) δ 145.2, 144.6, 144.3, 137.0, 132.9,
3
3
3
8
32.8, 132.3, 130.8, 129.8, 129.4, 129.2, 128.4, 128.2, 126.0, 125.3,
24.1, 122.8, 120.3, 29.3, 29.0, 25.6, 23.6, 23.2, 22.4 ppm. Elemental
13 1
H), 1.22−1.17 (m, 2H), 0.92 (t, J = 6.4 Hz, 3H) ppm. C { H}
) δ 135.1, 134.7, 129.4, 127.9, 33.2, 31.9,
analysis (%) calcd for 4, C H N I: C, 70.65; H, 6.78; N, 4.19;
NMR (100 MHz, CDCl
3
3
9
45
2
found: C, 69.39; H, 6.93; N, 4.45. For the cationic part of 4; HRMS
29.2, 24.4, 22.7, 14.1, 12.1 ppm.
+
+
(
5
ESI-TOF): m/z calcd. for C H N [M ] 541.3577; found:
General Procedure for Catalytic Hydrosilylation of Alkene
in Gram Scale. In a 30 mL J. Young pressure tube, 132.5 mg (0.223
mmol) of [Ni(PLY) (THF) ] was taken and dried under vacuum for
3
9
45
2
41.3571. For the anionic part of 4; HRMS (ESI-TOF): m/z calcd.
−
−
for I [M ]: 126.9039; found: 126.9046.
2
2
General Procedure for Stoichiometric Hydrodehalogena-
tion of Aryl Halides. A 15 mL J. Young pressure tube was charged
with a magnetic bar and aryl halide (0.05 mmol) to keep under
vacuum for 1 h. It was taken inside a glovebox, and DMF was added
to it. 60 mg (0.11 mmol) of 2 was taken in another vial and directly
added to the J. Young pressure tube. The color of the reaction mixture
immediately turned into red. Next, the tube was capped and stirred
for 36 h at room temperature. On completion, the reaction mixture
was diluted by adding 50 mL of ethyl acetate. The ethyl acetate part
was washed with water (100 mL × 3) and collected over anhydrous
Na SO . Ethyl acetate was removed under vacuum using a rotary
1 h. It was transferred to a glovebox to add 362 mg (0.668 mmol) of
, followed by the addition of 5 mL of THF. The color of the solution
2
immediately turned into dark green. It was stirred for 10 min at room
temperature inside the glovebox. Next, Ph SiH (1.67 mL, 8.91
2
2
mmol) and 1-octene (1.4 mL, 8.91 mmol) were added to it. It was
capped properly and stirred at room temperature for 6 h. On
completion, THF was removed under vacuum from the reaction
mixture and it was directly loaded to a column after dilution with
hexane. Octyldiphenylsilane was isolated through silica (100−200
1
mesh) using hexane as an eluent, and it was characterized using H,
2
4
1
3
evaporator. The hydrodehalogenated products were isolated by
passing the reaction mixture through a silica column (100−200
mesh) using ethyl acetate:hexane (1:100) as an eluent. Solvent was
removed under vacuum, and all the isolated hydrodehalogenated
C NMR spectroscopy which matched well with the reported
39
values. A colorless liquid was obtained (2.47 g, yield 94%).
44
General Procedure for Catalytic Borylation of CO2. Inside
an argon filled glovebox, a 15 mL pressure tube equipped with a J.
Young valve and PTFE screw cap was charged with a magnetic bar, 2
1
13
products were characterized by H and C NMR spectroscopy.
4
8
(
Benzyloxy)benzene (5a). Obtained as a colorless oil. 8.3 mg.
(
2 mg, 0.0037 mmol), 9-BBN (451.5 mg, 3.7 mmol), and
1
Yield 90%. H NMR (400 MHz, CDCl ): δ 7.45 (d, J = 8.8 Hz, 2H),
3
tetrahydrofuran (2 mL). The tube was tightly capped and taken out
of glovebox to pass through two freeze-pump-thaw cycles. To the
7
2
1
.42−7.38 (m, 2H), 7.35−7.29 (m, 3H), 7.01−6.98 (m, 2H), 5.08 (s,
H) ppm; 13C {1H} NMR (100 MHz, CDCl ): δ 158.8, 137.1, 129.5,
3
thawing solution, CO was purged at 25 °C. A PTFE screw cap was
2
28.6, 127.9, 127.5, 120.9, 114.8, 69.9 ppm.
4
9
tightly placed, and the reaction mixture was stirred for 16 h at 25 °C.
N,N-Dibenzylaniline (6a). Obtained as a pale yellow oil. 13.4 mg.
1
On completion of the reaction, solvent was evaporated under vacuum.
Yield 98%. H NMR (400 MHz, CDCl ): δ 7.34−7.30 (m, 4H),
3
1
11
13
7
4
1
.26−7.24 (m, 6H), 7.17−7.15 (m, 2H), 6.75−6.68 (m, 3H), 4.65 (s,
Finally, the product was analyzed by H, B, and C NMR
spectroscopic measurements. Yields were calculated using hexame-
H) ppm; 13C { H} NMR (100 MHz, CDCl ): δ 149.2, 138.6, 129.2,
1
3
1
28.6, 126.9, 126.7, 116.7, 112.5, 54.2 ppm.
thylbenzene as an internal standard using H NMR spectroscopy.
5
0
1
-Phenyl-1H-pyrrole (7a). Obtained as a white solid. 6.9 mg.
X-ray Crystallographic Details. Suitable single crystals of 1−4
were selected and mounted under a nitrogen atmosphere using the X-
TEMP2, and intensity data were collected on a Super Nova, Dual, Cu
at zero, Eos diffractometer. All the crystals were kept at 100 K during
1
Yield 96%. H NMR (400 MHz, CDCl ): δ 7.46−7.40 (m, 4H),
3
7
.28−7.24 (m, 1H), 7.12−7.11 (m, 2H), 6.38−6.37 (m, 2H) ppm;
13
1
C { H} NMR (100 MHz, CDCl ): δ 140.8, 129.5, 125.6, 120.5,
3
52
1
19.3, 110.4 ppm.
data collection. Using Olex2, the structure was solved with the
4
7
1
-Methyl-1H-indole (8a). Obtained as a colorless liquid. 5.6 mg.
53
ShelXT structure solution program using Intrinsic Phasing and
1
Yield 85%. H NMR (500 MHz, CDCl ): δ 7.62 (dt, J = 8 Hz, 1 Hz),
54
3
refined with the ShelXL refinement package using Least Squares
7
7
{
.31 (dd, J = 8 Hz, 1 Hz), 7.23−7.20 (m, 1H), 7.15−7.08 (m, 1H),
minimization. All nonhydrogen atoms were refined with anisotropic
displacement parameters. Crystallographic data (including structure
factors) for the structures have been deposited with the Cambridge
Crystallographic Data Centre. Copies of the data can be obtained free
and 1978719 contain the supplementary crystallographic data of
compounds 2, 3, and 4, respectively, for this paper.
13
.03 (d, J = 3 Hz), 6.48 (dd, J = 3 Hz, 1 Hz), 3.77 (s, 3H) ppm;
C
1
H} NMR (125 MHz, CDCl ): δ 136.8, 128.7, 128.5, 121.4, 120.8,
3
1
19.2, 109.1, 100.9, 32.8 ppm.
51
Phenanthrene (9a). Obtained as a white solid. 7.5 mg. Yield
1
8
4%. H NMR (500 MHz, CDCl ): δ 8.70 (d, J = 8 Hz, 2H), 7.90 (d,
3
J = 8 Hz, 2H), 7.75 (s, 2H), 7.67 (t, J = 7 Hz, 2H), 7.61 (t, J = 7 Hz,
1
2
1
H) ppm; 13C { H} NMR (125 MHz, CDCl ): δ 132.0, 130.3, 128.6,
3
26.9, 126.6, 122.6 ppm.
1
250
J. Org. Chem. 2021, 86, 1246−1252