Organometallics
Article
3
t
1.19 (4H, m, ring), 1.16 (18H, d, JHP = 17.3 Hz, Bu), 1.11 (18H, d,
7.21 (2H, d, J = 3.6 Hz, ArH), 4.83 (2H, t, J = 1.8 Hz, bridgehead),
and 3.52 ppm (2H, d, J = 1.7 Hz, ethano bridge). 13C{1H} NMR (101
MHz, CDCl3): δ 170.1 (CO), 140.7 (ArCq), 138.2 (ArCq), 127.9
(ArC), 127.3 (ArC), 125.3 (ArC), 124.5 (ArC), 48.1 (CH), and 45.5
ppm (CH).
3JHP = 17.7 Hz, Bu), and 0.90−0.75 ppm (4H, m, ring). 13C{1H}
NMR (101 MHz, CDCl3): δ 44.4 (dd, JCP = 19.4 Hz, JCP = 7.9 Hz,
t
1
2
2
1
CH2), 33.5 (d, JCP = 10.9 Hz, CH2), 31.9 (d, JCP = 21.4 Hz,
C(CH3)3), 31.3 (d, 1JCP = 19.2 Hz, C(CH3)3), 30.0 (d, 2JCP = 10.3 Hz,
2
2
9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-dime-
thanol. The title compound was synthesized according to a literature
procedure.35 Recrystallization from hot EtOH yielded fine white
needles. Yield: 6.2 g (54%). 1H NMR (400 MHz, d6-DMSO): δ 7.31−
CH3), 29.8 (d, JCP = 10.6 Hz, CH3), 26.3, and 25.9 ppm (d, JCP
=
20.9 Hz, CH). 31P{1H} NMR (162 MHz, CDCl3): δ 21.6 ppm. HR-
MS (+ve ESI, CH3CN): m/z (calcd), [M + H]+ 401.3461; found,
401.3476. Anal. Calcd for C24H50P2: C, 71.96; H, 12.58. Found: C,
71.01; H, 12.39.
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7.25 (4H, m, ArH), 7.11−7.06 (4H, m, ArH), 4.63 (2H, t, JHH = 4.9
Hz, OH), 4.44 (2H, s, CH), 3.30−3.23 (2H, m, CH2), 2.78−2.72 (2H,
m, CH2), and 2.08−2.01 ppm (2H, m, CH). 13C{1H} NMR (101
MHz, d6-DMSO): δ 144.10 (ArCq), 141.3 (ArCq), 125.4 (ArC), 125.3
(ArC), 125.1 (ArC), 123.2 (ArC), 60.2 (CH2OH), 45.6 (CH), and
42.9 ppm (CH).
(2-Methylenepropane-1,3-diyl)bis(di-tert-butylphosphine)
(5). This compound was synthesized according to the procedure for 4
using 3-chloro-2-chloromethyl-1-propene (0.20 g, 1.6 mmol), tBu2PH·
BH3 (0.53 g, 3.3 mmol), and n-BuLi (2.0 M in cyclohexane, 1.66 mL,
1
3.3 mmol) in THF (10 mL). White solid. Yield: 0.22 g (40%). H
NMR (400 MHz, CDCl3): δ 5.02 (2H, s -CCH2), 2.47 (4H, d, 2JHP
9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-bis-
(methylene) Bis(tosylate). Tosyl chloride (2.99 g, 15.7 mmol) was
added slowly in portions to a solution of 9,10-dihydro-9,10-
ethanoanthracene-11,12-diyl)-cis-dimethanol (1.67 g, 6.27 mmol) in
pyridine (10 mL) at 0 °C, with the temperature maintained below 5
°C during the course of addition. The mixture was then warmed to
room temperature and stirred for 1 h. The reaction mixture was then
poured onto 2 M HCl (70 mL) and stirred until the precipitate was no
longer sticky. The product was collected via filtration and washed with
H2O (3 × 15 mL). Recrystallization in an acetone/MeOH mixture
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t
= 4.1 Hz, −CH2-), and 1.4 ppm (36H, d, JHP = 10.9 Hz, Bu).
13C{1H} NMR (101 MHz, CDCl3): δ 148.5 (Cq, t, JPC = 11.7 Hz),
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113.9 (CH2C−, t, 3JPC = 10.0 Hz), 32.0 (Cq, d, 1JPC = 21.9 Hz), 30.6
1
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(−CH2−, dd, JPC = 23.9 Hz and JPC = 7.8 Hz), and 30.0 ppm
(C(CH3)3 d, JPC = 13.4 Hz). 31P{1H} NMR (162 MHz, CDCl3): δ
2
22.0 ppm. HR-MS (+ve ESI, CH3CN): m/z (calcd), [M + H]+
345.2835; found, 345.2839.
Bis[(di-tert-butylphosphino)methyl]dimethylsilane (6). This
compound was synthesized according to the procedure for 4 using
bis(chloromethyl)dimethylsilane (0.93 g, 0.86 mL, 5.95 mmol),
tBu2PH·BH3 (2.0 g, 12.5 mmol), and n-BuLi (2.0 M in cyclohexane,
6.25 mL, 12.5 mmol) in THF (10 mL). (Note: this compound could
not be purified over silica/alumina, as it was found to decompose to
di-tert-butylmethylphosphine; instead, it was purified by recrystalliza-
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gave the product as white crystalline plates. Yield: 2.3 g (65%). H
NMR (400 MHz, CDCl3): δ 7.79−7.73 (4H, m, ArH), 7.40−7.35
(4H, m, ArH), 7.24 (2H, dd, J = 5.4, 3.3 Hz, ArH), 7.10 (2H, dd, J =
5.4, 3.2 Hz, ArH), 7.00−6.93 (4H, m, ArH), 4.27 (2H, d, J = 1.5 Hz,
bridgehead), 3.73 (2H, dd, J = 9.5, 4.7 Hz, CH2), 3.33 (1H, t, J = 9.5
Hz, CH2), 2.48 (6H, s, CH3), and 2.45−2.36 ppm (2H, m, ethano
bridge). 13C{1H} NMR (101 MHz, CDCl3): δ 144.1 (ArCq), 141.1
(ArCq), 130.1 (ArCq), 128.1 (ArCq), 126.1 (ArCH), 125.9, (ArCH),
125.4 (ArCH), 123.7 (ArCH), 70.9 (CH2O), 47.5, and 46.7 ppm. HR-
MS (+ve ESI, CH3CN): m/z (calcd), [M + Na]+ 597.1376; found,
597.1377.
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tion from hot methanol.) White solid. Yield: 1.5 g (67%). H NMR
(400 MHz, CDCl3): δ 1.08 (36H, d, 3JHP = 12.7 Hz, tBu), 0.54 (4H, d,
2JHP = 14.0 Hz, CH2), and 0.17 ppm (6H, s, Si(CH3)2). 13C{1H} NMR
(101 MHz, CDCl3): δ 31.7 (Cq, d, 1JPC = 23.7 Hz), 29.7 (C(CH3)3, d,
2JPC = 14.0 Hz), 6.3 (CH2, dd, 1JPC = 42.0), and −0.06 ppm (Si(CH3)2,
t, 3JPC = 4.2 Hz). 31P{1H} NMR (162 MHz, CDCl3): δ 18.3 ppm. HR-
MS (+ve ESI, CH3CN): m/z (calcd), [M + H]+ 377.2917; found,
377.2923. Anal. Calcd for C20H46P2Si: C, 63.78; H, 12.31. Found: C,
63.69; H, 12.04.
cis-11,12-Bis((di-tert-butylphosphino)methyl)-9,10-dihydro-
9,10-ethanoanthracene (10). This compound was synthesized
using a procedure similar to that for 4, starting with 9,10-dihydro-9,10-
ethanoanthracene-11,12-diyl)-cis-bis(methylene) bis(tosylate) (1.50
g). The dphosphine−borane adduct was purified over silica gel
(10% EtOAc in hexane) to yield a white microcrystalline solid. Yield:
1,3-Bis(di-tert-butylphosphino)propane (8). This compound
was synthesized according to the procedure for 4 using n-BuLi (2.0 M
in cyclohexane, 3.12 mL, 6.25 mmol), tBuPH·BH3 (1.0 g, 6.25 mmol),
1,3-dibromopropane (0.30 mL, 2.98 mmol), THF (10 mL), and
pyrrolidine (10 mL). Colorless oil. Yield: 0.55 g (56%). 1H NMR (400
MHz, CDCl3): δ 1.80−1.68 (2H, CH2), 1.50−1.45 (4H, m, PCH2),
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1.01 g (70%). H NMR (400 MHz, CDCl3): δ 7.39 (2H, dd, J = 5.3,
3.2 Hz, ArH), 7.34 (2H, dd, J = 5.3, 3.2 Hz, ArH), 7.13 (2H, dd, J =
5.4, 3.2 Hz, ArH), 7.09 (2H, dd, J = 5.4, 3.2 Hz, ArH), 4.95 (2H, s,
bridgehead), 2.61−2.55 (2H, m, CH2), 1.74 (2H, td, J = 14.8, 1.8 Hz,
CH2), 1.30 (18H, d, J = 12.8 Hz, tBu), 1.25 (18H, d, J = 12.0 Hz, tBu),
1.20−1.09 (2H, m, ethano bridge), and 0.78 ppm (6H, m br, BH3).
31P{1H} NMR (162 MHz, CDCl3): δ 43.5 ppm (d, J = 45.4 Hz). The
diphosphine was obtained via deprotection similar to that for 4.
Residual BH3−pyrrolidine adduct was removed by washing with
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t
and 1.12 ppm (36H, d, JHP = 10.9 Hz, Bu). 13C{1H} NMR (101
MHz, CDCl3): δ 31.3 (t, 2JCP = 25.6 Hz, CH2), 31.3 (d, 1JCP = 20.3 Hz,
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C(CH3)3), 29.8 (d, JCP = 13.4 Hz, CH3), and 23.5 ppm (dd, JCP
=
20.5 Hz, 3JCP = 13.4 Hz, PCH2). 31P{1H} NMR (162 MHz, CDCl3): δ
27.5 ppm. HR-MS (+ve ESI, CH3CN): m/z (calcd), [M + H]+
333.2835; found, 333.2844. Anal. Calcd for C19H42P2: C, 68.64; H,
12.73. Found: C, 68.46; H, 12.41.
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MeOH. White powder. Yield: 0.74 g (92.8%). H NMR (400 MHz,
CDCl3): δ 7.35−7.27 (4H, m, ArH), 7.13−7.02 (4H, m, ArH), 4.71
(2H, s, bridgehead), 2.24 (2H, s, CH2), 1.81−1.65 (2H, m, CH2), 1.13
(18H, d, J = 11.2 Hz, tBu), 1.12 (18H, d, J = 10.4 Hz, tBu), and 0.84−
0.67 ppm (2H, m, ethano bridge). 13C{1H} NMR (101 MHz, CDCl3):
δ 144.8 (Ar), 141.8 (Ar), 126.4 (Ar), 125.7 (Ar), 125.5 (Ar), 123.5
(Ar), 48.5 (d, J = 10.4 Hz, bridgehead), 40.9 (dd, J = 19.0, 6.7 Hz,
ethano bridge), 32.1 (d, J = 22.2 Hz, C(CH3)3), 31.6 (d, J = 19.1 Hz,
C(CH3)3), 30.2 (d, J = 12.7 Hz, CH3), 30.2 (d, J = 13.1 Hz, CH3), and
22.9 ppm (d, J = 21.7 Hz, CH2P). 31P{1H} NMR (162 MHz, CDCl3):
δ 20.7 ppm. HR-MS (+ve ESI, CH3CN): m/z (calcd), [M + H]+
523.362; found, 523.3573. Anal. Calcd for C34H52P2: C, 78.12; H,
10.03. Found: C, 77.57; H, 9.71.
9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarbox-
ylic Acid. This compound was prepared from anthracene (10.0 g, 56.1
mmol) and fumaric acid (2.17 g, 18.7 mmol) in dioxane according to a
literature procedure.63 Off-white solid. 1H NMR (400 MHz, d6-
DMSO): δ 12.9 (2H, br. s, CO2H), 7.41−7.38 (2H, m, ArH), 7.27−
7.25 (2H, m, ArH), 7.13−7.06 (2H, m, ArH), 4.72 (2H, s, CH), and
1,4-Bis(di-tert-butylphosphino)butane (9). This compound
was synthesized according to the procedure for 4 using n-BuLi (2.0
t
M in cyclohexane, 3.12 mL, 6.25 mmol), BuPH·BH3 (1.0 g, 6.25
mmol), 1,4-dibromobutane (0.36 mL, 2.98 mmol), THF (10 mL), and
pyrrolidine (10 mL). White solid. Yield: 0.50 g (48%). 1H NMR (400
MHz, CDCl3): δ 1.66−1.57 (4H, m, CH2), 1.40−1.34 (4H, m, PCH2),
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and 1.11 ppm (36H, d, JHP = 10.8 Hz, Bu). 13C{1H} NMR (101
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MHz, CDCl3): δ 32.9 (d, JCP = 12.2 Hz, CH2), 32.6 (d, JCP = 12.2
Hz, CH2), 31.3 (d, 1JCP = 20.4 Hz, C(CH3)3), 29.8 (d, 2JCP = 13.5 Hz,
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CH3), and 21.1 ppm (d, JCP = 20.0 Hz, CH2). 31P{1H} NMR (162
MHz, CDCl3): δ 29.2 ppm. HR-MS (+ve ESI, CH3CN): m/z (calcd),
[M + H]+ 347.2991; found, 347.3000. Anal. Calcd for C20H44P2: C,
69.32; H, 12.80. Found: C, 69.19; H, 12.72.
9,10,11,15-Tetrahydro-9,10-[3,4]furanoanthracene-12,14-
dione. The title compound was synthesized according to a literature
procedure,62 yielding a tan microcrystalline solid. Yield: 12.6 g (91%).
1H NMR (400 MHz, CDCl3): δ 7.39 (2H, dd, J = 5.4, 3.2 Hz, ArH),
7.34 (2H, dd, J = 5.4, 3.2 Hz, ArH), 7.21 (2H, d, J = 3.7 Hz, ArH),
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Organometallics 2015, 34, 4281−4292