2182
M. Yus et al.
PAPER
13C NMR: = 65.65 (CH2), 86.95 (CO), 126.9 (2 C), 127.0 (3 C),
127.05, 127.8 (6 C), 128.25 (2 C), 128.8 (6 C), 139.1, 144.1 (3 C,
ArC).
1,4-Di(trityloxy)pentane (1j)
White solid; yield: 36%; mp 122 ºC; Rf 0.63 (hexane–EtOAc, 4:1).
IR (KBr): 3083, 3052, 3022, 1598, 1500 (HC=C), 1081, 1075 cm–1
(CO).
MS: m/z (%) = 273 (M+– 77, <4), 245 (18), 244 (100), 243 (85), 167
(11), 166 (16), 165 (68), 105 (51), 91 (88), 77 (27).
1H NMR: = 1.25 (d, 3 H, J = 6.1 Hz, MeCO), 1.00–1.68 (m, 4 H,
CH2CH2CO), 2.70–2.94 (m, 2 H, CH2O), 3.15–3.60 (m, 1 H, CHO),
7.12–7.31 (m, 18 H, ArH), 7.34–7.53 (m, 12 H, ArH).
13C NMR: = 21.1 (Me), 25.35 (CH2CH2O), 33.9 (CH2CHO),
63.85 (CH2O), 86.22 (CO), 86.44 (CO), 69.65 (CHO), 126.7 (6 C),
127.55 (6 C), 127.6 (9 C), 128.6 (9 C), 144.45 (3 C), 145.0 (3 C,
ArC).
Geranyl Trityl Ether (1e)22
Colourless oil; yield: 73%; Rf 0.71 (hexane–EtOAc, 4:1).
IR (neat): 3085, 3058, 3022, 1688, 1597, 1490 (HC=C), 1054 cm–1
(CO).
1H NMR: = 1.46 (s, 3 H, CH3), 1.61 (s, 3 H, CH3), 1.69 (s, 3 H,
CH3), 2.04–2.10 (m, 4 H, CH2CH2), 3.60 (d, 2 H, J = 6.3 Hz,
CH2O), 5.09–5.11 (m, 1 H, HC=CMe2), 5.42–5.46 (m, 1 H, CHCO),
7.15–7.19 (m, 9 H, ArH), 7.48–7.72 (m, 6 H, ArH).
13C NMR: = 14.1 (Me), 16.5 (Me), 25.7 (Me), 26.4 (CH2CH2),
39.55 (CH2CH2), 61.3 (CH2O), 86.0 (CO), 121.35 (CHCO), 124.1
(CH=CMe2), 131.55 (CMe2), 138.45 (CH2C=C), 126.8 (3 C), 127.7
(6 C), 128.7 (6 C), 144.4 (3 C, ArC).
MS (DIP): m/z (%) = 588 (M+, <1), 244 (70), 243 (100), 165 (56),
105 (28).
Anal. Calcd for C43H40O2: C, 87.3; H, 6.8. Found: C, 87.7; H, 6.8.
Dimethyl(3-trityloxypropyl)amine (1k)
White solid; yield: 50%; mp 75 ºC; Rf 0.72 (hexane–EtOAc, 4:1)
IR (KBr): 3085, 3055, 3031, 1595, 1489 (HC=C), 1089, 1060 cm–1
(CO).
1H NMR: = 1.70–1.87 (m, 2 H, CH2CO), 2.22 (s, 6 H, 2 × MeN),
2.37 (t, 2 H, J = 7.8 Hz, CH2N), 3.11 (t, 2 H, J = 6.5 Hz, CH2O),
7.12–7.35 (m, 9 H, ArH), 7.37–7.55 (m, 6 H, ArH).
MS: m/z (%) = 319 (M+ – 77, <1), 244 (39), 243 (100), 165 (34),
105 (11), 69 (11).
9-Trityloxy-1-nonanol (1f)23
Colourless oil; yield: 47%; Rf 0.20 (hexane–EtOAc, 4:1).
13C NMR: = 28.35 (CH2CO), 45.4 (2 C, 2 × MeN), 56.9 (CH2N),
62.1 (CH2O), 86.4 (CO), 126.8 (3 C), 127.8 (6 C), 128.65 (6 C),
144.5 (3 C, ArC).
IR (neat): 3086, 3058, 3032, 3022, 1600, 1490 (HC=C), 1088, 1071
cm–1 (CO).
1H NMR: = 1.11–1.71 [m, 15 H, (CH2)7CO and OH], 3.04 (t, 2 H,
J = 6.6 Hz, CH2OTr), 3.62 (t, 2 H, J = 6.6 Hz, CH2OH), 7.41–7.35
(m, 9 H, ArH), 7.38–7.51 (m, 6 H, ArH).
MS: m/z (%) = 344 (M+, <1), 243 (10), 165 (12), 102 (100), 58 (90).
HRMS: m/z calcd for C24H27NO, 345.2013; found, 345.1900.
13C NMR:
= 25.7, 26.25, 29.35, 29.4, 29.5, 30.0, 32.8
Diethyl(4-trityloxypentyl)amine (1l)
Colourless oil; yield: 23%; Rf 0.74 (hexane–EtOAc, 4:1).
IR (neat): 3083, 3062, 3026, 1598, 1495 (HC=C), 1086 cm–1 (CO).
[(CH2)7CO)], 63.1 (CH2OH), 63.65 (CH2OTr), 86.25 (CO), 126.76
(3 C), 127.65 (6 C), 127.91 (6 C), 144.5 (3 C, ArC).
MS: m/z (%) = 402 (M+, <1), 323 (10), 259 (19), 244 (36), 243
1H NMR: = 0.94 (d, 3 H, J = 6.1 Hz, MeCO), 1.02 (t, 6 H, J = 7.1
Hz, 2 × CH3CH2), 1.25–1.46 [m, 4 H, (CH2)2CO], 2.24 (t, 2 H,
J = 4.3 Hz, CH2CH2N), 2.54 (m, 4 H, 2 × MeCH2), 3.55–3.65 (m, 1
H, CHO), 7.16–7.34 (m, 9 H, ArH), 7.40–7.49 (m, 6 H, ArH).
(100), 183 (47), 166 (11), 165 (60), 105 (69), 77 (15), 55 (13).
1,9-Di(trityloxy)nonane (1h)
White solid; yield: 36%; mp 91 ºC; Rf 0.65 (hexane–EtOAc, 4:1).
IR (KBr): 3084, 3056, 3031, 1488 (HC=C), 1089, 1076 cm–1 (CO).
13C NMR: = 11.0 (2 C, 2 × CH3CH2), 21.25 (CH2CH2CO), 21.4
(CH3CO), 35.05 (CH2CO), 46.5 (2 C, 2 × CH2Me), 52.45
(CH2CH2N), 76.6 (CHO), 86.5 (CO), 126.8 (3 C), 127.6 (6 C),
128.95 (6 C), 145.45 (3 C, ArC).
1H NMR: = 1.12–1.41 [m, 10 H, (CH2)5CH2CO], 1.53–1.68 (m, 4
H, 2 × CH2CO), 3.02 (t, 4 H, J = 6.6 Hz, 2 × CH2O), 7.14–7.34 (m,
18 H, ArH), 7.39–7.51 (m, 12 H, ArH).
13C NMR: = 22.6 (2 C), 26.25, 29.45 (2 C), 30.05 (2 C)
[(CH2)7CO], 63.65 (2 C, 2 × CH2O), 86.25 (2 C, 2 × CO), 126.75 (6
C), 127.65 (12 C), 128.7 (12 C), 144.55 (6 C, ArC).
MS: m/z (%) = 401 (M+, <1), 243 (15), 165 (27), 158 (60), 86 (100).
HRMS: m/z calcd for C28H35NO, 401.2719; found, 401.2678.
MS: m/z (%) = 644 (M+,<1), 567 (15), 401 (23), 245 (13), 244 (89),
1-Methoxy-9-trityloxynonane (1g)
9-Trityloxy-1-nonanol (1f) was prepared from 1,9-nonanediol as
described above. A solution of alcohol 1f (1.206 g, 3.0 mmol) in an-
hyd THF (5 mL) was added dropwise to a stirred suspension of NaH
(73 mg, 3.0 mmol) in THF (10 mL) under Ar at 0 ºC. When the hy-
drogen evolution was finished, MeI (0.2 mL, 3.0 mmol) was added
at 0 ºC and the reaction mixture was stirred for 24 h at r.t. The reac-
tion was quenched with water (5 mL) at 0ºC and extracted with
EtOAc (3 × 15 mL). The combined organic phases were washed
with brine (5 mL) and dried over sodium sulfate. After evaporation
of the solvents, pure compound 1g was obtained in almost quantita-
tive yield.
243 (100), 183 (31), 165 (55), 105 (38).
HRMS: m/z calcd for C47H48O2, 644.3654; found, 644.3574.
1-Trityloxy-2-octanol (1i)24
Colourless oil; yield: 63%; Rf 0.42 (hexane–EtOAc, 4:1).
IR (neat): 3422 (OH), 3093, 3053, 3046, 1602, 1488 (HC=C), 1088,
1078 cm–1 (CO).
1H NMR: = 0.86 (t, 3 H, J = 6.7 Hz, Me), 1.10–1.50 [m, 11 H,
(CH2)5 and OH], 3.02 (dd, 1 H, J = 9.3, 7.6 Hz, CHHO), 3.17 (dd, 1
H, J = 9.3, 3.3 Hz, CHHO), 3.71–3.80 (m, 1 H, CHO), 7.11–7.35
(m, 9 H, ArH), 7.37–7.45 (m, 6 H, ArH).
Colourless oil; yield: >99%; Rf 0.60 (hexane–EtOAc, 4:1).
13C NMR: = 14.05 (Me), 22.55, 25.4, 29.25, 31.7, 33.3 [(CH2)5],
67.75 (CH2O), 70.95 (CHO), 86.6 (CO), 127.05 (3 C), 127.8 (6 C),
128.6 (6 C), 143.9 (3 C, ArC).
IR (neat): 3088, 3067, 3021, 1608, 1495 (HC=C), 1089, 1071 cm–1
(CO).
1H NMR: = 1.20–1.42 (m, 10 H, (CH2)7CO) , 1.48–1.67 [m, 4 H,
(CH2)7CO], 3.04 (t, 2 H, J = 6.6 Hz, CH2OTr), 3.32 (s, 3 H, Me),
MS: m/z (%) = 388 (M+, <1), 244 (40), 243 (100), 183 (12), 165
(42), 105 (17).
Synthesis 2003, No. 14, 2179–2184 © Thieme Stuttgart · New York