P. Knochel et al.
FULL PAPER
1490, 1377, 1352, 986, 772, 698 cmÀ1; 1H NMR (300 MHz, CDCl3): d 7.76
(d, J 9 Hz, 2H), 7.52 7.03 (m, 7H), 4.01 3.92 (m, 1H), 3.86 3.77 (m,
1H), 2.54 2.31 (m, 2H), 2.12 2.00 ppm (m, 2H); 13C NMR (75 MHz,
CDCl3): d 140.2, 137.2, 132.5, 128.1, 127.4, 127.3, 125.5, 62.9, 40.0, 23.5,
anti-5,5-Dimethyl-1-phenyl-1,4-hexanediol (6h): According to general
procedure C, (2-tert-butyl-1-cyclobuten-1-yl)benzene (558 mg, 3 mmol)
was treated with BH3 ¥ THF at 408C for 16 h to give 6h as a colourless
oil. Yield: 460 mg (69%). The desired diol was obtained as a diastereo-
meric mixture of 80:20. The benzylic H-C(OH) signal has a chemical shift
of 79.3 ppm, whereas the diastereomeric syn-1,4-diol has a chemical shift of
18.8 ppm; MS (EI): m/z (%): 310 (11) [M] , 214 (100), 201 (14), 130 (7), 106
(6); HRMS calcd for C17H17F3O2: 310.1181; found: 310.1178.
79.0 ppm. IR film: nÄ 3480, 3080, 3024, 2960, 2924, 1342, 1055, 702 cmÀ1
;
anti-1-[4-(Aminomethyl)phenyl]-4-phenyl-1,4-butanediol (6c): According
to general procedure C, 4-(2-phenyl-1-cyclobuten-1-yl)benzonitrile
(693 mg, 3 mmol) was treated with BH3 ¥ THF at 508C for 5 h to give 6c
as a colourless oil. Yield: 577 mg (71%). The desired diol was obtained as
one diastereoisomer. The benzylic H-C(OH) signal has a chemical shift of
72.2 ppm, whereas the diastereomeric syn-1,4-diol has a chemical shift of
1H NMR (300 MHz, CDCl3): d 7.27 7.10 (m, 5H), 4.71 4.67 (m, 0.8H),
4.62 4.58 (m, 0.2H), 3.20 3.15 (m, 0.8H), 3.13 3.11 (m, 0.2H), 1.94 1.18
(m, 4H), 0.82 (s, 1.8H), 0.80 ppm (s, 7.2H); 13C NMR (75 MHz, CDCl3):
d 144.1, 127.4, 126.3, 124.8, 79.3, 79.0, 73.9, 73.1, 36.4, 35.6, 34.9, 34.0, 27.5,
26.3, 24.7 ppm; MS (EI): m/z (%): 222 (3) [M] , 204 (7), 186 (2), 147 (100),
120 (81), 107 (58), 91 (56), 70 (38), 57 (24); HRMS calcd for C14H22O2:
222.1620; found: 222.1638.
71.3 ppm. IR (film): nÄ 3340, 2855, 1603, 1450, 1357, 1027, 971, 701 cmÀ1
;
1H NMR (300 MHz, DMSO): d 7.34 7.23 (m, 9H), 4.53 4.51 (m, 2H),
3.74 (s, 2H), 2.56 2.54 (m, 2H), 1.70 1.56 ppm (m, 4H); 13C NMR
(75 MHz, DMSO): d 146.7, 144.7, 142.1, 128.2, 127.1, 126.9, 126.1, 125.9,
anti-1-Dimethylphenylsilyl-4-phenyl-1,4-butanediol (6i): According to
general procedure C, dimethylphenyl-(2-phenyl-1-cyclobuten-1-yl)silane
(792 mg, 3 mmol) was treated with BH3 ¥ THF at 508C for 5 h to give 6i
as a colourless oil. Yield: 621 mg (69%). The desired diol was obtained as
one diastereoisomer. The benzylic H-C(OH) signal has a chemical shift
74.2 ppm, of whereas the diastereomeric syn-1,4-diol has a chemical shift of
72.8, 72.7, 45.6, 36.2, 36.0 ppm; MS (APCI): m/z (%): 270 (5) [M] , 254 (47),
199 (100); HRMS calcd for C17H21NO2: 271.1572; found: 271.1585.
anti-1-(4-Methoxyphenyl)-4-phenyl-1,4-butanediol (6d): According to
general procedure C, 1-methoxy-4-(2-phenyl-1-cyclobuten-1-yl)benzene
(708 mg, 3 mmol) was treated with BH3 ¥ THF at 508C for 5 h to give 6d
as a colourless oil. Yield: 726 mg (89%). The desired diol was obtained as
one diastereoisomer. The benzylic H-C(OH) signal has a chemical shift of
73.9 ppm, whereas the diastereomeric syn-1,4-diol has a chemical shift of
73.1 ppm. IR (KBr): nÄ 3367, 3060, 3028, 2962, 2930, 1493, 1453, 1375, 1106,
74.8 ppm. IR film: nÄ 3328, 2945, 2867, 1464, 1028, 883, 833, 663 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.27 6.89 (m, 11H), 4.64 4.60 (m, 1H),
3.49 3.42 (m, 1H), 1.91 1.59 (m, 4H), 0.00 ppm (s, 6H); 13C NMR
(75 MHz, CDCl3): d 140.9, 136.5, 134.4, 134.1, 129.1, 127.9, 127.5, 126.2,
74.2, 55.0, 32.6, 15.6, 1.0 ppm; MS (EI): m/z (%): 300 (19) [M] , 283 (24),
266 (100), 165 (33), 131 (11); HRMS calcd for C18H24O2Si: 300.1546; found:
300.1528.
757, 704 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.27 7.12 (m, H), 6.80
6.75 (m, H), 4.65 4.53 (m, 2H), 3.70 (s, 3H), 2.50 (brs, 2H), 1.84 1.66 ppm
anti-5,8-Tridecanediol (6j): According to general procedure C, 1-butyl-2-
pentyl-1-cyclobutene (540 mg, 3 mmol) was treated with BH3 ¥ THFat 408C
for 16 h to give 6j as a colourless solid. Yield: 512 mg (79%). The desired
diol was obtained as one diastereoisomer. One H-C(OH) signal has a
chemical shift of 70.9 ppm, whereas the diastereomeric syn-1,4-diol has a
chemical shift of 72.2 ppm. M.p.: 898C; IR (KBr): nÄ 3402, 1960, 1637,
(m, 4H); 13C NMR (75 MHz, CDCl3): d 159.4, 145.0, 137.1, 128.8, 127.5,
126.2, 114.2, 74.2, 73.9, 55.7, 35.6, 35.4 ppm; MS (EI): m/z (%): 254 (1) [M] ,
179 (2), 130 (84), 104 (100), 91 (42), 77(28), 51 (12); HRMS calcd for
C17H20O3: 272.1412; found: 272.1432.
anti-1-Phenyl-1,4-pentanediol (6e): According to general procedure C, (2-
methyl-1-cyclobuten-1-yl)benzene (432 mg, 3 mmol) was treated with
BH3 ¥ THF at 408C for 16 h to give 6e as a colourless oil. Yield: 427 mg
(79%). The desired diol was obtained as one diastereoisomer. The benzylic
H-C(OH) signal has a chemical shift of 74.4 ppm, whereas the diastereo-
meric syn-1,4-diol has a chemical shift of 74.7 ppm. IR film: nÄ 3351, 2960,
1453, 1059, 698 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 3.57 3.55 (m,
2H),1.59 1.23 (m, 16H), 0.86 0.80 ppm (m, 6H); 13C NMR (75 MHz,
CDCl3): d 70.9, 70.8, 36.5, 36.2, 32.2, 30.9, 27.0, 24.4, 21.7, 21.6, 13.1,
13.0 ppm; MS (EI): m/z (%): 215 (1) [M] , 173 (10), 155 (16), 141 (54), 123
(69), 109 (100), 95 (31), 81 (79), 69 (75), 55 (93); HRMS calcd for C13H28O2:
216.2089; found: 216.2078.
2874, 1602, 1453, 1029, 700 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.29
7.19 (m, 5H), 4.67 (t, J 6.3 Hz, 1H), 3.87 3.74 (m, 1H), 2.11 (brs, 2H),
1.86 1.74 (m, 2H), 1.64 1.33 (m, 2H), 1.05 ppm (d, J 6.2 Hz, 3H);
13C NMR (75 MHz, CDCl3): d 145.0, 128.8, 127.9, 126.2, 74.4, 68.3, 35.5,
anti-5,8-Dodecanediol (6k): According to general procedure C, 1,2-
dibutyl-1-cyclobutene (498 mg, 3 mmol) was treated with BH3 ¥ THF at
408C for 16 h to give 6k as a colourless solid. Yield: 509 mg (84%). The
desired diol was obtained as one diastereoisomer. The H-C(OH) signal has
a chemical shift of 72.4 ppm, whereas the diastereomeric syn-1,4-diol has a
chemical shift of 72.0 ppm. M.p.: 948C; IR (KBr): nÄ 3337, 2955, 1636,
35.4, 23.9 ppm; MS (EI): m/z (%): 180 (1) [M] , 141 (13), 120 (56), 107
(100), 91 (13), 79 (63), 56 (13); HRMS calcd for C11H16O2: 180.1150; found:
180.1144.
1466, 1128, 1042 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 3.59 3.57 (m,
anti-1-Phenyl-1,4-hexanediol (6 f): According to general procedure C, (2-
ethyl-1-cyclobuten-1-yl)benzene (474 mg, 3 mmol) was treated with BH3 ¥
THF at 408C for 16 h to give 6 f as a colourless oil. Yield: 477 mg (82%).
The desired diol was obtained as one diastereoisomer. The benzylic
H-C(OH) signal has a chemical shift of 74.4 ppm, whereas the diastereo-
meric syn-1,4-diol has a chemical shift of 74.7 ppm. IR film: nÄ 3351, 2960,
2H), 2.06 (s, 2H), 1.61 1.23 (m, 12H), 0.84 pm (t, J 7 Hz, 3H); 13C NMR
(75 MHz, CDCl3): d 72.4, 37.6, 33.6, 28.3, 23.1, 14.4 pm; MS (EI): m/z
(%): 202 (1) [M] , 183 (1), 127 (77), 109 (100), 83 (14), 70 (38), 57 (25);
HRMS calcd for C12H26O2: 202.1933; found: 202.1946.
anti-1,4-Diferrocenyl-1,4-butandiol (6l): According to general procedure
C, (2-ferrocenyl-1-cyclobuten-1-yl)ferrocene (1.27 g, 3 mmol) was treated
with BH3 ¥ THF at 508C for 5 h to give 6l as a red solid. Yield: 893 mg
(65%). The desired diol was obtained as one diastereoisomer. The
H-C(OH) signal has a chemical shift of 77.9 ppm, whereas the diastereo-
meric syn-1,4-diol has a chemical shift of 77.1 ppm. M.p.: 1248C; IR (KBr):
2874, 1602, 1453, 1029, 700 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.34
7.16 (m, 5H), 4.66 (t, J 6 Hz, 1H), 3.55 3.47 (m, 1H), 1.81 (q, J 7 Hz,
2H), 1.64 1.33 (m, 4H), 0.85 ppm (t, J 9 Hz, 3H); 13C NMR (75 MHz,
CDCl3): d 144.6, 128.2, 127.2, 125.6, 74.2, 73.0, 34.6, 32.6, 30.0, 9.74 ppm;
MS (EI): m/z (%): 194 (5) [M] , 176 (14), 147 (30), 120 (68), 107 (100), 91
nÄ 3391, 3089, 2915, 1409, 1105, 1022, 811 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d 4.17 3.92 (m, 18H), 2.30 2.18 (m, 2H), 1.49 4.46 (m, 2H),
(20), 79 (51), 55 (8); HRMS calcd For C12H18O2: 194.1307; found: 194.1328.
anti-5-Methyl-1-phenyl-1,4-hexanediol (6g): According to general proce-
dure C, (2-isopropyl-1-cyclobuten-1-yl)benzene (516 mg. 3 mmol) was
treated with BH3 ¥ THF at 408C for 16 h to give 6g as a colourless oil.
Yield: 449 mg (72%). The desired diol was obtained as a diastereomeric
mixture of 95:5. The benzylic H-C(OH) signal has a chemical shift of
74.8 ppm, whereas the diastereomeric syn-1,4-diol has a chemical shift of
75.5 ppm. IR film: nÄ 3422, 3067, 3041, 3011, 2998, 2967, 2874, 1939, 1855,
1.19 1.17 ppm (m, 2H); 13C NMR (75 MHz, CDCl3): d 88.3, 77.9, 68.0,
67.3, 66.0, 32.2 ppm; MS (EI): m/z (%): 440 (100) [M À H2O] , 438 (16), 267
(10), 226 (23), 207 (49), 186 (25), 120 (34), 73 (24); HRMS calcd for
C24H26Fe2O2: 458.0632; found: 458.0626.
1800, 1602, 1494, 1352, 1045, 997, 763, 740, 719, 609 cmÀ1 1H NMR
;
(300 MHz, CDCl3) d 7.28 7.15 (m, 5H), 4.67 4.56 (m, 1H), 3.48 3.50
(m, 1H), 1.85 1.74 (m, 2H), 1.57 1.25 (m, 4H), 1.14 0.99 (m, 1H), 0.84
0.75 ppm (m, 6H); 13C NMR (75 MHz, CDCl3): d 145.2, 128.8, 127.7,
126.2, 74.8, 74.2, 40.6, 36.2, 30.7, 26.2, 13.9, 12.2 ppm; MS (EI): m/z (%): 222
(2) [M] , 204 (10), 147 (76), 129 (39), 120 (90), 107 (100), 91 (52), 79 (43), 70
(28), 57 (14); HRMS calcd for C13H20O2: 208.1463; found: 208.1446.
Acknowledgement
We thank the DFG (SPP 1118) for generous support. We thank also the
BASF AG, Bayer AG, Chemetall GmbH and Degussa AG for the generous
gift of chemicals.
5264
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2003, 9, 5259 5265