3H), 6.67 (d, J = 8.8 Hz, 2H), 7.14 (d, J = 8.8 Hz, 2H); 13C{1H}
NMR (100 MHz, CD3OD) -5.7, 18.2, 25.7, 55.2, 66.5, 81.1, 81.9,
113.2, 128.3, 128.5, 159.5; MS (EI) m/z 394 (M+), 337 (100%)
25.7, 66.0, 80.6, 82.4, 114.1, 126.5, 128.1, 146.5; MS (EI) m/z
379 (M+), 322 (100%)
4.2.6. N-2,3-Propanediol-4-(12-hydoxymethyl-1,12-
dicarba-closo-dodecaborane-1-yl)aniline (7)
4.2.2. 1-Hydroxymethyl-12-(4-hydroxyphenyl)-1,12-
dicarba-closo-dodecaborane (10)
To a solution of 12 (50 mg, 0.13 mmol) in ethanol (3 mL)
was added glycidol (11.7 mg, 0.16 mmol) at room temperature.
The mixture was stirred at 80 ºC for 48 h, before the solvent was
removed under reduced pressure. Purification by column
chromatography on silica gel (eluent: n-hexane / AcOEt = 5/1 to
2/1, v/v) gave N-2,3-propanediol-4-(12-tert-butyldimethylsiloxy-
methyl-1,12-dicarba-closo-dodecaborane-1-yl)aniline (23 mg,
A 1 M solution of BBr3 in CH2Cl2 (0.36 mL, 0.36 mmol) was
added dropwise to a solution of 9 (20 mg, 0.05 mmol) in CH2Cl2
(1 mL) at 0 ºC under Ar atmosphere, before the reaction mixture
was stirred at room temperature for 16 h. The reaction was
quenched with water and the reaction mixture was extracted with
CH2Cl2. The organic layer was washed with brine, dried over
Na2SO4, and concentrated. Purification by column
chromatography on silica gel (eluent: n-hexane to n-
hexane/AcOEt = 10/1, v/v) gave 10 (16.6 mg, 0.07 mmol) as a
colorless solid in quantitative yield; 1H NMR (400 MHz,
CD3OD) 1.00–3.50 (brm, 10H), 3.55 (s, 2H), 4.96 (brs, 1H), 6.61
(d, J = 8.8 Hz, 2H), 7.06 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (100
MHz, CD3OD) 66.1, 82.7, 83.6, 115.6, 128.6, 129.6, 129.3,
158.6; MS (EI) m/z 266 (M+), 250 (100%).
1
0.05 mmol) as a colorless solid in 39% yield; H NMR (400
MHz, CDCl3) -0.02 (s, 6H), 0.85 (s, 9H), 1.00–3.50 (brm, 10H),
3.12 (dd, J = 7.3 Hz, 13.2 Hz, 1H), 3.22 (dd, J = 4.4 Hz, 13.2 Hz,
1H), 3.49 (s, 2H), 3.60 (dd, J = 5.6 Hz, 11.2 Hz, 1H), 3.74 (dd, J
= 3.5 Hz, 11.2 Hz, 1H), 3.88–3.95 (m, 1H), 6.41 (d, J = 8.8 Hz,
2H), 7.00 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3)
-5.6, 18.2, 25.7, 46.4, 64.7, 66.1, 70.2, 80.7, 82.4, 112.4, 126.3,
128.1, 147.7; MS (EI) m/z 453 (M+), 393 (100%). A 1 M
solution of TBAF in THF (0.07 mL, 0.07 mmol) was added to a
solution of N-2,3-propanediol-4-(12-tert-butyldimethylsiloxy-
methyl-1,12-dicarba-closo-dodecaborane-1-yl)aniline (20 mg,
0.04 mmol) in 1 mL of dry THF, before the reaction mixture was
stirred at room temperature for 24 h. The reaction was quenched
with water and the reaction mixture was extracted with AcOEt.
The organic layer was washed with brine, dried over MgSO4,
and concentrated. Purification by column chromatography on
silica gel (eluent: n-hexane/AcOEt = 1/1 to 1/2, v/v) gave 7 (10
mg, 0.03 mmol) as a colorless solid in 75% yield; Colorless
cubes (CHCl3); mp 137.5–139.0 ºC; 1H NMR (400 MHz, CDCl3)
1.00–3.50 (brm, 10H), 3.13 (dd, J = 7.8 Hz, 13.2 Hz, 1H), 3.24
(dd, J = 4.4 Hz, 13.2 Hz, 1H), 3.54 (brs, 2H), 3.61 (dd, J = 5.9
Hz, 11.2 Hz, 1H), 3.75 (dd, J = 3.3 Hz, 11.2 Hz, 1H), 3.89–3.95
(m, 1H), 6.42 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H);
13C{1H} NMR (100 MHz, CD3OD) 47.3, 65.4, 66.2, 71.6, 82.5,
84.5, 112.9, 125.7, 128.9, 150.3; MS (EI) m/z 339 (M+), 278
(100%); HRMS Calcd for C12H25B10NO3: 339.2839; Found:
339.2836; Anal. Calcd for C12H25B10NO3: C, 42.46; H, 7.42; N,
4.13; Found: C, 42.17; H, 7.27; N, 4.32.
4.2.3. 1-Hydroxymethyl-12-{4-(2,3-
dihydroxypropyloxy)phenyl}-1,12-dicarba-closo-
dodecaborane (6a)
To a solution of 10 (200 mg, 0.76 mmol) in DMF (5 mL) was
added 3-chloro-1,2-propanediol (76 L, 0.91 mmol) and K2CO3
(130 mg, 0.91 mmol) at room temperature under Ar atmosphere.
The mixture was heated at 80 ºC for 8h, before 3-chloro-1,2-
propanediol (456 L, 5.47 mmol) and K2CO3 (455 mg, 3.19
mmol) were further added. The reaction was continued for 40 h
until 10 was disappeared on TLC. After cooling, the reaction was
quenched with water and the reaction mixture was extracted with
AcOEt. The organic layer was washed with brine, dried over
Na2SO4, and concentrated. Purification by column
chromatography on silica gel (eluent: n-hexane/AcOEt = 10/1 to
5/1, v/v) gave 6a (236 mg, 0.69 mmol) as a colorless solid in
1
91% yield; Colorless prisms (MeOH); mp 144.0–146.0 ºC; H
NMR (400 MHz, CD3OD) 1.00–3.50 (brm, 10H), 3.46 (s, 2H),
3.58–3.66 (m, 2H), 3.88–3.94 (m, 2H), 3.97–4.02 (m, 1H), 6.77
(d, J = 9.3 Hz, 2H), 7.12 (d, J = 9.3 Hz, 2H); 13C{1H} NMR (100
MHz, CD3OD) 64.1, 66.2, 70.4, 71.7, 83.3, 115.0, 115.9, 129.4,
130.0, 160.6. MS (EI) m/z 340 (M+), 266 (100%); HRMS Calcd
for C12H24B10O4: 340.2678, Found: 340.2677; Anal. Calcd for
C12H24B10O4: C, 42.35; H, 7.06; Found: C, 42.34; H, 7.11.
4.2.7. 1-{4-(2,3-Dihydroxypropyloxy)phenyl}-1,12-
dicarba-closo-dodecaborane (6c)
Compound 6c was prepared by the same method as described
for the synthesis of 6a using 1311 (0.33 g, 1.31 mmol) instead of
10; 330 mg (0.80 mmol, 80% yield); Colorless needles (n-
4.2.4. 1-tert-Butyldimethylsiloxymethyl-12-(4-
nitrophenyl)-1,12-dicarba-closo-dodecaborane (11)
1
hexane/ CH2Cl2); mp 81.0–83.0 ºC; H NMR (400 MHz,CDCl3)
Compound 11 was prepared by the same method as described
for the synthesis of 9 using 4-iodonitrobenzene (0.33 g, 1.31
mmol) instead of 4-iodoanisole; 330 mg (0.80 mmol, 80%
1.00–3.50 (brm, 10H), 1.89 (t, J = 5.9 Hz, 1H), 2.45 (d, J = 4.9
Hz, 1H), 2.76 (brs, 1H), 3.71 (dd, J = 5.9 Hz, 11.2 Hz, 1H),
3.78–3.84 (m, 1H), 3.97–3.98 (m, 2H), 4.05–4.08 (m, 1H), 6.69
(d, J = 8.8 Hz, 2H), 7.12 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (100
MHz, CDCl3) 59.3, 63.5, 69.1, 70.2, 86.1, 113.8, 128.3, 130.0,
158.3; MS (EI) m/z 310 (M+), 236 (100%); HRMS Calcd for
C11H22B10O3: 310.2573; Found: 340.2566; Anal. Calcd for
C11H22B10NO3: C, 42.56; H, 7.14; Found: C, 42.66; H, 7.17.
1
yield); H NMR (400 MHz, CDCl3) -0.01 (s, 6H), 0.86 (s, 9H),
1.00–3.50 (brm, 10H), 3.50 (s, 2H), 7.38 (d, J = 8.8 Hz, 2H),
8.03 (d, J = 8.8 Hz, 2H); 13C{1H}NMR (100 MHz, CDCl3) -5.7,
18.2, 25.6, 66.0, 79.9, 83.0, 123.2, 128.4, 142.9, 147.6; MS (EI)
m/z 411 (M+), 73 (100%).
4.2.5. 4-(12-tert-Butyldimethylsiloxymethyl-1,12-
dicarba-closo-dodecaborane-1-yl)aniline (12)
4.2.8. 1-{4-(1,3-Dioxolane-2,2-dimethyl-4-
methyloxy)phenyl}-1,12-dicarba-closo-
dodecaborane (14)
A catalytic amount of Pd/C (80 mg) was added to a solution
of 11 (400 mg, 0.97 mmol) in methanol (10 mL), before the
mixture was stirred at room temperature for 3 h under H2
atmosphere. Pd/C was removed by filtration through Celite,
before the filtrate was evaporated. Purification by column
chromatography on silica gel (eluent: n-hexane/AcOEt = 100/1
to 20/1, v/v) gave 12 (401 mg, 1.06 mmol) as a colorless solid in
A solution of 6c (1.0 g, 3.23 mmol) and TsOH (80 mg, 0.46
mmol) in acetone (10 mL) was stirred at room temperature for 4
h, before the reaction was quenched with saturated aq. NaHCO3
and the mixture was extracted with AcOEt. The organic layer
was washed with brine, dried over Na2SO4, and concentrated.
Purification by column chromatography on silica gel (eluent: n-
hexane/AcOEt = 10/1 to 1/1, v/v) gave 14 (994 mg, 2.84 mmol)
as a colorless solid in 88% yield. Colorless thin needles (n-
1
quantitative yield; H NMR (400 MHz, CDCl3) 1.00–3.50 (brm,
10H), 3.49 (s, 2H), 3.63 (brs, 2H), 6.44 (d, J = 8.8 Hz, 2H), 6.97
(d, J = 8.8 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) -5.7, 18.1,