J.-Y. Lu et al. / Tetrahedron xxx (2015) 1e9
7
11B NMR (160 MHz, CDCl3):
d
ꢀ2.38 (d, J¼148.4 Hz, 1B), ꢀ5.85 (d,
d
ꢀ2.42 (d, J¼148.8 Hz, 1B), ꢀ5.89 (d, J¼149.9 Hz, 1B), ꢀ7.79 to
J¼144.4 Hz, 1B), ꢀ8.03 to ꢀ21.98 (m, 8B). FTIR (KBr, cmꢀ1):
n
3066,
ꢀ18.64 (m, 8B). FTIR (KBr, cmꢀ1):
n 3059, 2960, 2940, 2862, 2589,
2975, 2930, 2860, 2660, 2596, 1510, 1444, 1398, 722. EIMS [MþH]þ
m/z 293.3. Anal. Calcd for C13H26B10: C, 53.76; H, 9.02. Found: C,
54.07; H, 9.48.
1444, 1398, 1350, 722. EIMS [MþH]þ m/z 231.2. Anal. Calcd for
C8H24B10: C, 42.07; H, 10.59. Found: C, 42.70; H, 10.85.
4.2.12. 1-(6-Phenyl-1-hexyl)-1,2-dicarba-closo-dodecaborane
4.2.6. 1-(3-Methyl-1-butyl)-1,2-dicarba-closo-dodecaborane
(3ch). Eluent: hexane. Yield 45% (68 mg). White solid,
(3aj).10a Eluent: hexane. Yield 95% (102 mg). Colorless liquid. 1H
mp¼35e36 ꢁC. 1H NMR (500 MHz, CDCl3):
d
7.27 (t, J¼7.6 Hz, 2H),
NMR (CDCl3, 500 MHz, ppm):
d
3.49 (s, 1H), 2.13 (t, 2H, J¼8.5 Hz,
7.17 (dd, J¼14.1, 7.3 Hz, 3H), 3.51 (s, 1H), 2.61e2.56 (m, 2H),
2.18e2.13 (m, 2H), 1.59 (dt, J¼15.2, 7.6 Hz, 2H), 1.47e1.39 (m, 2H),
1.29 (ddd, J¼15.4, 10.1, 3.9 Hz, 4H). 13C NMR (126 MHz, CDCl3):
clustereCH2e), 1.46e1.38 (m, 1H, eCHe), 1.28e1.24 (m, 2H,
eCH2e), 0.80 (d, 6H, J¼6.6 Hz, e(CH3)2). 13C NMR (CDCl3, 125 MHz,
ppm):
d
62.1, 47.4, 24.4, 22.6, 18.1, 14.2, 8.7. 11B NMR (CDCl3,
d 142.45, 128.41, 128.34, 125.77, 75.44, 60.98, 38.09, 35.82, 31.18,
160 MHz, ppm):
d
ꢀ2.4 (d, J¼148.3 Hz, 1B), ꢀ5.9 (d, J¼147.8 Hz, 1B),
29.12, 28.83, 28.71. 11B NMR (160 MHz, CDCl3):
J¼148.6 Hz, 1B), ꢀ5.86 (d, J¼145.9 Hz, 1B), ꢀ8.15 to ꢀ17.09 (m, 8B).
d
ꢀ2.38 (d,
ꢀ8.8e(ꢀ13.6) (m, 8B). FTIR (KBr, cmꢀ1):
n 3066, 2960, 2933, 2873,
2593, 1468, 1388, 1369, 723. EIMS [MþH]þ m/z 217.2. Anal. Calcd for
FTIR (KBr, cmꢀ1):
n 3068, 2990, 2908, 2850, 2612, 2555, 1605, 1456,
C7H22B10: C, 39.22; H, 10.34. Found: C, 39.88; H, 10.24.
1380, 722. EIMS [MþH]þ m/z 307.3. Anal. Calcd for C14H28B10: C,
55.22; H, 9.27. Found: C, 55.63; H, 9.48.
4.2.7. 1-(3-Methyl-1-pentyl)-1,2-dicarba-closo-dodecaborane
(3ak). Eluent: hexane. Yield 97% (111 mg). Colorless liquid. 1H NMR
4.2.13. 1-(4-Methyl-1-hexyl)-1,2-dicarba-closo-dodecaborane
(500 MHz, CDCl3):
1H), 1.28 (dt, J¼15.0, 6.1 Hz, 3H), 1.19e1.07 (m, 1H), 0.89e0.81 (m,
6H). 13C NMR (126 MHz, CDCl3):
75.72, 60.97, 35.83, 35.68, 33.89,
29.01, 18.89, 11.14. 11B NMR (160 MHz, CDCl3):
ꢀ2.44 (d,
J¼149.0 Hz, 1B), ꢀ5.92 (d, J¼147.2 Hz, 1B), (ꢀ8.25)e(ꢀ14.62) (m,
d
3.57 (s, 1H), 2.24e2.15 (m, 2H), 1.50e1.41 (m,
(3ck). Eluent: hexane. Yield 62% (75 mg). Colorless liquid. 1H NMR
(500 MHz, CDCl3):
d
3.56 (s, 1H), 2.17 (ddd, J¼10.9, 5.9, 4.7 Hz, 2H),
d
1.53e1.36 (m, 2H), 1.35e1.20 (m, 3H), 1.18e1.01 (m, 2H), 0.85 (t,
d
J¼6.9 Hz, 6H). 13C NMR (126 MHz, CDCl3):
d 75.54, 60.97, 38.39,
35.75, 34.05, 29.32, 26.87, 19.01, 11.32. 11B NMR (160 MHz, CDCl3):
8B). FTIR (KBr, cmꢀ1):
n
3060, 2955, 2920, 2883, 2590, 1466, 1390,
d
ꢀ2.41 (d, J¼149.3 Hz, 1B), ꢀ6.43 (t, J¼161.3 Hz, 1B), ꢀ8.86 to
1370, 722. EIMS [MþH]þ m/z 231.2. Anal. Calcd for C8H24B10: C,
ꢀ13.67 (m, 8B). FTIR (KBr, cmꢀ1):
n 3058, 2958, 2925, 2894, 2605,
42.07; H, 10.59. Found: C, 42.36; H, 10.84.
1455, 1390, 1366, 723. EIMS [MþH]þ m/z 245.3. Anal. Calcd for
C9H26B10: C, 44.59; H, 10.81. Found: C, 44.82; H, 11.14.
4.2.8. 1-(2-Cyclobutyl-1-ethyl)-1,2-dicarba-closo-dodecaborane
(3al). Eluent: hexane. Yield 92% (104 mg). Colorless liquid. 1H NMR
4.2.14. 1-(4,4-Dimethyl-1-pentyl)-1,2-dicarba-closo-dodecaborane
(CDCl3, 500 MHz, ppm):
2.08e2.00 (m, 5H), 1.86e1.81 (m, 2H), 1.57e1.51 (m, 3H). 13C NMR
(CDCl3, 125 MHz, ppm):
75.3, 60.9, 36.2, 35.7, 34.9, 27.8, 18.2. 11
d
3.54 (s, 1H, CclustereH), 2.16e2.13 (m, 1H),
(3co). Eluent: hexane. Yield 72% (87 mg). White solid,
mp¼52e53 ꢁC. 1H NMR (500 MHz, CDCl3):
d 3.56 (s, 1H), 2.18e2.13
d
B
(m, 2H), 1.45e1.37 (m, 2H), 1.14e1.08 (m, 2H), 0.87 (s, 9H). 13C NMR
NMR (CDCl3, 160 MHz, ppm):
d
ꢀ2.3 (d, J¼148.7 Hz, 1B), ꢀ5.9 (d,
(126 MHz, CDCl3): d 75.59, 61.03, 43.17, 38.87, 30.32, 29.24, 24.60.
J¼149.3 Hz, 1B), ꢀ8.8e(ꢀ13.6) (m, 8B). FTIR (KBr, cmꢀ1):
n
3066,
11B NMR (160 MHz, CDCl3):
d
ꢀ2.36 (d, J¼148.7 Hz, 1B), ꢀ5.86 (d,
2955, 2931, 2861, 2593, 1454, 1441, 1369, 723. EIMS [MþH]þ m/z
229.2. Anal. Calcd for C8H22B10: C, 42.45; H, 9.80. Found: C, 42.60; H,
9.96.
J¼146.6 Hz, 1B), ꢀ8.13 to ꢀ14.22 (m, 8B). FTIR (KBr, cmꢀ1):
n 3055,
2942, 2945, 2901, 2595, 1460, 1401, 1350, 722. EIMS [MþH]þ m/z
245.3. Anal. Calcd for C9H26B10: C, 44.59; H, 10.81. Found: C, 44.91;
H, 11.25.
4.2.9. 1-(2-Cyclopentyl-1-ethyl)-1,2-dicarba-closo-dodecaborane
(3am). Eluent: hexane. Yield 81% (97 mg). Colorless liquid. 1H NMR
4.2.15. 1-(2-Phenyl-1-ethyl)-1,2-dicarba-closo-dodecaborane
(CDCl3, 500 MHz, ppm):
d
3.56 (s, 1H, CclustereH), 2.21e2.18 (m, 2H,
(6aa). Eluent: hexane. Yield 89% (110 mg). White solid,
clustereCH2e), 1.75e1.69 (m, 2H), 1.66e1.63 (m, 1H), 1.61e1.58 (m,
mp¼80e81 ꢁC. 1H NMR (500 MHz, CDCl3):
d
7.28 (t, J¼7.4 Hz, 2H),
2H), 1.53e1.49 (m, 2H), 1.47e1.42 (m, 2H), 1.05e1.01 (m, 2H). 13C
7.21 (dd, J¼8.1, 6.6 Hz, 1H), 7.10 (d, J¼7.2 Hz, 2H), 3.56 (s, 1H),
NMR (CDCl3,125 MHz, ppm): d 75.5, 60.9, 39.3, 37.4, 35.5, 32.4, 25.0.
2.78e2.72 (m, 2H), 2.49e2.44 (m, 2H). 13C NMR (126 MHz, CDCl3):
11B NMR (CDCl3, 160 MHz, ppm):
d
ꢀ2.3 (d, J¼148.7 Hz, 1B), ꢀ5.9 (d,
d
138.62, 128.75, 128.10, 126.80, 74.63, 61.16, 39.68, 35.26. 11B NMR
J¼145.7 Hz, 1B), ꢀ8.8e(ꢀ13.6) (m, 8B). FTIR (KBr, cmꢀ1):
n
3065,
(160 MHz, CDCl3):
d
ꢀ2.19 (d, J¼148.7 Hz, 1B), ꢀ5.62 (d,
2952, 2865, 2592, 1454, 1370, 723. EIMS [MþH]þ m/z 243.2. Anal.
J¼144.7 Hz, 1B), ꢀ7.77 to ꢀ15.44 (m, 8B). FTIR (KBr, cmꢀ1):
n 3050,
Calcd for C9H24B10: C, 44.97; H, 10.06. Found: C, 45.20; H, 10.42.
2980, 2915, 2845, 2625, 2540, 1615, 1460, 1384, 723. EIMS [MþH]þ
m/z 251.2. Anal. Calcd for C10H20B10: C, 48.36; H, 8.12. Found: C,
48.70; H, 8.53.
4.2.10. 1-(2-Cyclohexyl-1-ethyl)-1,2-dicarba-closo-dodecaborane
(3an). Eluent: hexane. Yield 83% (105 mg). Colorless liquid. 1H NMR
(CDCl3, 500 MHz, ppm):
clustereCH2e), 1.70e1.62 (m, 5H), 1.35e1.30 (m, 2H), 1.20e1.11 (m,
4H), 0.90e0.83 (m, 2H). 13C NMR (CDCl3, 125 MHz, ppm):
75.7,
60.8, 37.1, 36.5, 35.7, 32.9, 26.3, 26.0. 11B NMR (CDCl3, 160 MHz,
d
3.55 (s, 1H, CclustereH), 2.22e2.19 (m, 2H,
4.2.16. 1-[2-(4-Methylphenyl)-1-ethyl]-1,2-dicarba-closo-dodecabor-
ane (6ab). Eluent: hexane. Yield 91% (119 mg). White solid,
d
mp¼91e92 ꢁC. 1H NMR (500 MHz, CDCl3):
d
7.14 (d, J¼7.7 Hz, 2H),
7.04 (d, J¼7.8 Hz, 2H), 3.59 (s, 1H), 2.78e2.73 (m, 2H), 2.52e2.47 (m,
ppm):
d
ꢀ2.4 (d, J¼147.2 Hz, 1B), ꢀ5.9 (d, J¼140.3 Hz, 1B),
2H), 2.35 (s, 3H). 13C NMR (126 MHz, CDCl3):
129.52, 128.05, 74.82, 61.20, 39.91, 34.92, 21.06. 11B NMR (160 MHz,
d 136.52, 135.66,
ꢀ8.8e(ꢀ13.6) (m, 8B). FTIR (KBr, cmꢀ1):
n 3065, 2925, 2853, 2592,
1449, 1373, 723. EIMS [MþH]þ m/z 257.3. Anal. Calcd for C10H26B10
:
CDCl3):
d
ꢀ2.15 (d, J¼149.0 Hz, 1B), ꢀ5.59 (d, J¼145.1 Hz, 1B), ꢀ6.72
C, 47.21; H, 10.30. Found: C, 47.70; H, 10.58.
to ꢀ15.87 (m, 8B). FTIR (KBr, cmꢀ1):
n 3066, 2985, 2920, 2855, 2610,
2560, 2550, 1610, 1465, 1377, 722. EIMS [MþH]þ m/z 265.2. Anal.
4.2.11. 1-(3,3-Dimethyl-1-butyl)-1,2-dicarba-closo-dodecaborane
Calcd for C11H22B10: C, 50.35; H, 8.45. Found: C, 50.66; H, 8.80.
(3ao). Eluent: hexane. Yield 93% (106 mg). White solid,
mp¼75e76 ꢁC. 1H NMR (500 MHz, CDCl3):
d
3.57 (s, 1H), 2.20e2.15
4.2.17. 1-[2-(4-Fluorophenyl)-1-ethyl]-1,2-dicarba-closo-dodecabor-
(m, 2H), 1.36e1.30 (m, 2H), 0.86 (s, 9H). 13C NMR (126 MHz, CDCl3):
ane (6ac). Eluent: hexane. Yield 81% (108 mg). White solid,
d
75.76, 60.96, 42.78, 33.58, 30.09, 29.01. 11B NMR (160 MHz, CDCl3):
mp¼52e53 ꢁC. 1H NMR (500 MHz, CDCl3):
7.11 (dd, J¼8.4, 5.4 Hz,
d