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4.2.29. 1-(5-Ethyl-5-triethylsilyloxyheptyl)-12-{2-(trans-5-hydr
oxy-2,2-dimethyl-1,3-dioxan-4-yl)ethoxymethyl}-1,12-dicarba-
closo-dodecaborane (39)
4.2.33. 1-(5-Ethyl-5-hydroxyheptyl)-12-(3,4,5-trihydroxypentyl
oxy)methyl-1,12-dicarba-closo-dodecaborane (43)
1 M HCl (1.0 mL) was added to a solution of 39 (23.0 mg,
0.039 mmol) in MeOH/THF 1:1 (2.0 mL) at 0 °C, and then the mix-
ture stirred for 1.5 h at room temperature. The mixture was diluted
with ethyl acetate, then the organic layer was washed with water
and brine, dried with Na2SO4 and concentrated. Purification by sil-
ica gel column chromatography (eluent: n-hexane/ethyl acetate;
1:1) to give 43 (15.0 mg, 88%) as colorless oil. 1H NMR (500 MHz,
CDCl3) d 3.81 (m, 1H), 3.77 (m, 2H), 3.54 (m, 3H), 3.33 (d,
J = 10.7 Hz, 1H), 3.30 (d, J = 10.7 Hz, 1H), 3.04 (d, J = 3.0 Hz, 1H),
2.80–1.50 (br m, 10H), 2.57 (d, J = 6.0 Hz, 1H), 2.14 (t, J = 5.8 Hz,
1H), 1.77 (m, 2H), 1.61 (t, J = 7.6 Hz, 2H), 1.40 (q, J = 7.5 Hz, 4H),
1.28 (t, J = 7.8 Hz, 2H), 1.11 (m, 4H), 1.00 (s, 1H), 0.81 (t,
J = 7.5 Hz, 6H).
Under H2 atomosphere, 20% Pd(OH)2/C (88.0 mg) was added to
37 (882 mg, 0.130 mmol) in THF (30 mL) and stirred for 30 min at
room temperature. Insoluble materials were filtrated off and the
filtrate was concentrated, then the crude product was purified by
silica gel column chromatography (eluent: n-hexane/ethyl acetate;
10:1) to give 39 (685 mg, 90%) as colorless oil. 1H NMR (500 MHz,
CDCl3) d 3.90 (dd, J = 11.3 Hz, 5.4 Hz, 1H), 3.62 (m, 1H), 3.60 (dd,
J = 11.3 Hz, 9.4 Hz, 1H), 3.44 (m, 3H), 3.34 (d, J = 10.7 Hz, 1H),
3.30 (d, J = 10.7 Hz, 1H), 2.80–1.50 (br m, 10H), 2.70 (d, J = 4.4 Hz,
1H), 1.90 (m, 1H), 1.75 (m, 1H), 1.60 (t, J = 8.0 Hz, 2H), 1.44 (s,
3H), 1.40 (q, J = 7.9 Hz, 4H), 1.36 (s, 3H), 1.25 (m, 2H), 1.09 (m,
4H), 0.91 (t, J = 7.9 Hz, 9H), 0.77 (t, J = 7.5 Hz, 6H), 0.53 (q,
J = 7.9 Hz, 6H).
13C NMR (125 MHz, CDCl3) d 7.71, 22.8, 30.0, 30.1, 32.2, 37.7,
37.9, 63.6, 70.4. 73.0, 73.6, 73.7, 74.4, 76.4, 81.0; LRMS (ESI+) 457
[(M+Na)+]; HRMS (ESI+) m/z 459.3866 [(M+Na)+: calcd for C17H42-
B10NaO5, 459.3859].
4.2.30. 1-(5-Ethyl-5-triethylsilyloxyheptyl)-12-{2-(cis-5-hydro
xy-2,2-dimethyl-1,3-dioxan-4-yl)ethoxymethyl}-1,12-dicarba-
closo-dodecaborane (40)
Compound 40 was prepared by the similar procedure that in
case of compound 39 but using compound 38 as a reaction sub-
strate (89%). 40: colorless oil, 1H NMR (500 MHz, CDCl3) d 4.06
(dd, J = 12.2 Hz, 2.2 Hz, 1H), 4.03 (m, 1H), 3.82 (dd, J = 12.2 Hz,
2.0 Hz, 1H), 3.36 (m, 2H), 3.33–3.26 (m, 3H), 2.80–1.50 (br m,
10H), 2.52 (d, J = 11.2 Hz, 1H), 1.76 (m, 2H), 1.60 (m, 2H), 1.46 (s,
3H), 1.37 (s, 3H), 1.36 (q, J = 7.8 Hz, 4H), 1.27 (m, 2H), 1.10 (m,
4H), 0.92 (t, J = 7.4 Hz, 9H), 0.77 (t, J = 7.8 Hz, 6H), 0.54 (q,
J = 7.4 Hz, 6H).
4.2.34. 1-(5-Ethyl-5-hydroxyheptyl)-12-(3,4,5-trihydroxypentyl
oxy)methyl-1,12-dicarba-closo-dodecaborane (44)
Compound 44 was prepared by the similar procedure that in
case of compound 43 but using compound 40 as a reaction sub-
strate (88%). Compound 44: colorless oil, 1H NMR (500 MHz, CDCl3)
d 3.83 (m, 1H), 3.73 (m, 2H), 3.53 (m, 2H), 3.50 (m, 1H), 3.31 (s, 2H),
3.08 (d, J = 3.2 Hz, 1H), 2.80–1.50 (br m, 10H), 2.75 (d, J = 3.6 Hz,
1H), 2.22 (dd J = 6.9 Hz, 5.1 Hz, 1H), 1.86 (m, 1H), 1.69 (m, 1H),
1.65 (m, 2H), 1.38 (q, J = 7.5 Hz, 4H), 1.27 (m, 2H), 1.10 (m, 4H),
0.99 (s, 1H), 0.80 (t, J = 7.5 Hz, 6H). 13C NMR (125 MHz, CDCl3) d
80.9, 74.4, 73.6, 73,5, 72.0, 70.0, 64.7, 37.9, 37.7, 32.8, 30.9, 30.0,
22.9, 7.7; LRMS (ESI+) 457 [(M+Na)+]; HRMS (ESI+) m/z 459.3865
[(M+Na)+: calcd for C17H42B10NaO5, 459.3859].
4.2.31. 1-(5-Ethyl-5-triethylsilyloxyheptyl)-12-{2-(trans-2,2-
dimethyl-5-methoxy-1,3-dioxan-4-yl)ethoxymethyl}-1,12-
dicarba-closo-dodecaborane (41)
NaH (4.0 mg, 0.102 mmol) was added to 39 (40.0 mg,
0.0679 mmol) in DMF (2.0 mL) and stirred for 10 min at 0 °C. Then
MeI (19.3 mg, 0.136 mmol) was added to the reaction mixture at
0 °C, and stirred at 0 °C for 30 min and at room temperature for
1 h. Then the reaction was quenched with water, and diluted with
ethyl acetate. The organic layer was washed with water and brine,
dried with Na2SO4 and concentrated. Purification by silica gel col-
umn chromatography (eluent: n-hexane/ethyl acetate; 10:1 to 5:1)
gave 36.2 mg (0.0600 mmol, 89%) of 41 as colorless oil. 1H NMR
(500 MHz, CDCl3) d 3.95 (dd, J = 11.5 Hz, 5.1 Hz, 1H), 3.66 (ddd,
J = 9.1 Hz, 9.1 Hz, 2.9 Hz, 1H), 3.60 (dd, J = 11.4 Hz, 9.1 Hz, 1H),
3.38 (m, 2H), 3.35 (s, 3H), 3.31 (d, J = 10.8 Hz, 1H), 3.25 (d,
J = 10.8 Hz, 1H), 3.01 (ddd, J = 9.1 Hz, 9.1 Hz, 5.1 Hz, 1H), 2.80–
1.50 (br m, 10H), 1.99 (m, 1H), 1.60 (m, 2H), 1.51 (m, 1H), 1.42
(s, 3H), 1.37 (q, J = 7.8 Hz, 4H), 1.34 (s, 3H), 1.26 (m, 2H), 1.07 (m,
4H), 0.90 (t, J = 7.4 Hz, 9H), 0.77 (t, J = 7.8 Hz, 6H), 0.51 (q,
J = 7.4 Hz, 6H).
4.2.35. 1-(5-Ethyl-5-hydroxyheptyl)-12-(3,5-dihydroxy-4-meth
oxypentyloxy)methyl-1,12-dicarba-closo-dodecaborane (45)
Compound 45 was prepared by the similar procedure that in
case of compound 43 but using compound 41 as a reaction sub-
strate (93%). 45: colorless oil, 1H NMR (500 MHz, CDCl3) d 3.88
(m, 1H), 3.79 (dd, J = 6.1 Hz, 4.4 Hz, 1H), 3.56 (m, 1H), 3.49 (ddd,
J = 9.0 Hz, 9.0 Hz, 4.0 Hz, 1H), 3.44 (s, 3H), 3.32 (d, J = 10.8 Hz,
1H), 3.29 (d, J = 10.8 Hz. 1H), 3.08 (m, 1H), 2.99 (d, J = 2.6 Hz, 1H),
2.80–1.50 (br m, 10H), 2.33 (t, J = 6.2 Hz, 1H), 2.05 (m, 1H), 1.74
(m, 1H), 1.63 (m, 2H), 1.39 (q, J = 7.4 Hz, 4H), 1.27 (m, 2H), 1.11
(m, 4H), 0.98 (s, 1H), 0.81 (t, J = 7.4 Hz, 6H). 13C NMR (125 MHz,
CDCl3) d 83.2, 80.9, 74.4, 73.6, 71.6, 70.6, 61.0, 57.8, 53,4, 37.9,
37.7, 32.6, 30.9, 30.0, 22.9, 7.71; LRMS (ESI+) 471 [(M+Na)+]; HRMS
(ESI+) m/z 473.4027 [(M+Na)+: calcd for
C18H44B10NaO5,
473.4015].
4.2.36. 1-(5-Ethyl-5-hydroxyheptyl)-12-(3,5-dihydroxy-4-meth
oxypentyloxy)methyl-1,12-dicarba-closo-dodecaborane (46)
Compound 46 was prepared by the similar procedure that in
case of compound 43 but using compound 42 as a reaction sub-
4.2.32. 1-(5-Ethyl-5-triethylsilyloxyheptyl)-12-{2-(cis-2,2-
dimethyl-5-methoxy-1,3-dioxan-4-yl)ethoxymethyl}-1,12-
dicarba-closo-dodecaborane (42)
Compound 42 was prepared by the similar procedure that in
case of compound 41 but using compound 40 as a reaction sub-
strate (97%). Compound 42: colorless oil, 1H NMR (500 MHz, CDCl3)
d 4.04 (d, J = 12.9 Hz, 2.0 Hz, 1H), 4.03 (m, 1H), 3.91 (dd, J = 12.9 Hz,
2.0 Hz, 1H), 3.41 (m, 1H), 3.38 (s, 3H), 3.33 (m, 1H), 3.29 (d,
J = 10.7 Hz, 1H), 3.25 (d, J = 10.7 Hz, 1H), 2.88 (ddd, J = 2.0 Hz,
2.0 Hz, 2.0 Hz, 1H), 2.80–1.50 (br m, 10H), 1.86 (m, 1H), 1.68 (m,
1H), 1.60 (m, 2H), 1.45 (s, 3H), 1.38 (s, 3H), 1.36 (q, J = 7.8 Hz,
4H), 1.27 (m, 2H), 1.08 (m, 4H), 0.91 (t, J = 7.4 Hz, 9H), 0.77 (t,
J = 7.8 Hz, 6H), 0.52 (q, J = 7.4 Hz, 6H).
strate (95%). 46: colorless oil, 1H NMR (500 MHz, CDCl3)
d
3.91(m, 1H), 3.85 (m, 1H), 3.68 (m, 1H), 3.50 (m, 2H), 3.48 (s,
3H), 3.30 (s, 2H), 3.20 (ddd, J = 4.5 Hz, 4.5 Hz, 4.5 Hz, 1H), 2.80–
1.50 (br m, 10H), 2.78 (d, J = 3.6 Hz, 1H), 2.17 (t, J = 6.0 Hz, 1H),
1.73 (m, 2H), 1.61 (m, 2H), 1.37 (q, J = 7.5 Hz, 4H), 1.27 (m, 2H),
1.10 (m, 4H), 0.98 (s, 1H), 0.80 (t, J = 7.5 Hz, 6H); 13C NMR
(125 MHz, CDCl3) d 82.2, 80.8, 74.3, 73.5, 70.7, 69.6, 61.2, 58.4,
37.9, 37.7, 32.3, 30.9, 30.0, 22.9, 7.71; LRMS (ESI+) 471
[(M + Na)+]; HRMS (ESI+) m/z 473.4029 [(M+Na)+: calcd for C18H44-
B10NaO5, 473.4015].