F. Orsini et al. / Tetrahedron: Asymmetry 12 (2001) 2961–2969
2965
13C NMR (CDCl3): 23.7 (t), 27.0 (t), 75.3 (d), 75.6 (d),
127.3 (d), 128.6 (d), 129.7 (d), 130.7 (d), 129.3 (s), 138.1
(2C) (s); MS (EI) m/z: 190 (M+), 146 (M+−CO2).
derivative 9 (0.055 g, 0.3 mmol, 10%) and by 1-chloro-
2-hydroxy derivative 10 (0225 g, 1.37 mmol, 45%).
Compound 6: Colorless oil, [h]D=−30.5 (c=1.98,
1
CHCl3); H NMR (CDCl3): l 1.88 (dddd, 1H, J=12.5,
Sodium azide (0.43 g, 6.6 mmol) was added to a
solution of the carbonate 5 (0.85 g, 4.4 mmol) in dry
DMF (20 mL). The resulting suspension was heated at
120°C in a pre-heated oil bath and the reaction was
monitored by thin layer chromatography (silica gel,
eluting with petroleum ether:ethyl acetate 7:3). After
ca.10 h, the reaction mixture was cooled, diluted with
water (20 mL) and extracted with ethyl acetate (3×20
mL). The combined organic extracts were dried
(Na2SO4) and the solvent removed under reduced pres-
sure. The crude material was flash-chromatographed
(silica gel, eluting with petroleum ether:ethyl acetate
7:3) to afford the azido alcohol 3 (0.80 g, 95%).
6.3, 6.3, 3.8 Hz, H-3), 2.35 (dddd, 1H, J=12.5, 8.8, 6.3,
6.3 Hz, H-3%), 2.45 (s, 3H, Me), 2.75 (ddd, 1H, J=17.5,
6.3, 6.3 Hz, H-4), 2.97 (ddd, 1H, J=17.5, 6.3, 6.3 Hz,
H-4%), 4.78 (d, 1H, J=3.8 Hz, H-1), 4.88 (ddd, 1H,
J=8.8, 3.8, 3.8 Hz, H-2), 7.05 (dd, 1H, J=7.0, 1.5 Hz,
H-5 or H-8), 7.20 (ddd, 2H, J=7.0, 7.0, 1.5 Hz, H-6,
H-7), 7.33 (dd, 1H, J=7.0, 1.5 Hz, H-8 or H-5), 7.34
(d, 2H, J=8.0 Hz, H-3%%, H-5%%), 7.84 (d, 2H, J=8.0 Hz,
H-2%%, H-6%%); 13C NMR (CDCl3): 21.5 (q), 23.8 (t), 26.2
(t), 68.6 (d), 80.9 (d), 126.4 (d), 127.7 (2C, d), 128.3 (2C,
d), 129.2 (d), 129.8 (2C, d), 133.8 (s), 135.1 (2C, s),
144.9 (s); MS (EI) m/z: 146 (M+−PTSH), 128 (M+−
PTSH–H2O). Calcd for C17H18O4S: C, 64.15; H, 5.66.
Found: C, 64.35; H, 6.01%.
4.2. (1S,2S)-2-Hydroxy-1-amino-1,2,3,4-tetra-
hydronaphthalene 4
4.4. (1S,2S)-1-Chloro-2-p-toluenesulphonyloxy-1,2,3,4-
tetrahydronaphthalene 9
A solution of (1S,2S)-2-hydroxy-1-azido-1,2,3,4-tetra-
hydronaphthalene 3 (0.64 g, 3.3 mmol) in methanol
(100 mL) was hydrogenated for 3 h in the presence
of 10% palladium on charcoal (0.26 g). The suspen-
sion was filtered on a Celite pad and the solvent re-
moved under reduced pressure. The crude mater-
ial was purified by column chromatography (silica
gel, eluting with chlorofom:methanol 95:5; chloro-
form:methanol:di-iso-propylamine 95:5:5) and afforded
pure (1S,2S)-2-hydroxy-1-amino-1,2,3,4-tetrahydro-
naphthalene 4 (0.435 g, 2.66 mmol, 80%). Compound 4:
Colorless crystals; mp=111–113°C (ethyl acetate–
petroleum ether); [h]D=−85.4 (c=0.634, CHCl3); 1H
NMR (CDCl3): l 1.81 (dddd, 1H, J=18.0, 4.0, 8.0, 4.0
Hz, H-3), 2.19 (dddd, 1H, J=18.0, 10.0, 8.0, 4.0 Hz,
H-3%), 2.91 (m, 2H, H-4, H-4%), 3.56 (ddd, 1H, J=10.0,
8.0, 4.0 Hz, H-2), 3.65 (d, 1H, J=8.0 Hz, H-1), 7.0–7.5
(m, 4H aromatic hydrogens); 13C NMR (CDCl3): 27.8
(t), 29.3 (t), 57.7 (d), 73.4 (d), 126.3 (d), 126.6 (d), 126.8
(d), 128.5 (d), 135.8 (s), 139.3 (s); MS (EI) m/z: 163
(M+), 146 (M+−NH3), 128 (M+−NH3–H2O). Calcd for
C10H13NO: C, 73.62; H, 7.98; N, 8.59. Found: C, 73.98;
H, 7.90; N, 8.31%.
Colorless crystals, mp=113–115°C (ethyl acetate–
petroleum ether); [h]D=−4.0 (c=1.98, CHCl3); 1H
NMR (CDCl3): l 1.99 (dddd, 1H, J=14.0, 6.0, 4.0, 4.0
Hz, H-3), 2.42 (dddd, 1H, J=14.0, 10.0, 6.0, 2.0 Hz,
H-3%), 2.45 (s, 3H, CH3), 2.80 (ddd, 1H, J=16.0, 6.0,
4.0 Hz, H-4), 2.87 (ddd, 1H, J=16.0, 10.0, 6.0 Hz,
H-4%), 5.06 (ddd, 1H, J=7.0, 4.0, 2.0 Hz, H-2), 5.07 (d,
1H, J=7.0 Hz, H-1), 7.10 (dd, 1H, J=7.1, 1.8 Hz, H-5
or H-8), 7.20 (ddd, 2H, J=7.1, 7.1, 1.8 Hz, H-6, H-7),
7.25 (dd, 2H, J=7.1, 1.8 Hz, H-8 or H-5), 7.32 (d, 2H,
J=8.0 Hz, H-3%%, H-5%%), 7.80 (d, 2H, J=8.0 Hz, H-2%%,
H-6%%); 13C NMR (CDCl3): 21.6 (q), 23.3 (t), 23.8 (t),
55.8 (d), 79.9 (d), 126.7 (d), 127.8 (2C, d), 128.7 (2C, d),
128.8 (2C, d), 130.8 (d), 132.3 (s), 134.0 (s), 135.2 (s),
145.1 (s); MS (EI) m/z: 336–338 (M++1), 301 (M+−Cl).
Calcd for C17H17ClO3S: C, 60.71; H, 5.06. Found: C,
60.75; H, 5.2%.
4.5. (1S,2S)-1-Chloro-2-hydroxy-1,2,3,4-tetrahydro-
naphthalene 10
Colorless oil; [h]D=−39 (c=0.7, CHCl3); 1H NMR
(CDCl3): l 1.99 (dddd, 1H, J=14.0, 6.0, 4.0, 4.0 Hz,
H-3), 2.21 (dddd, 1H, J=14.0, 10.0, 6.0, 2.0 Hz, H-3%),
2.95 (m, 2H, H-4, H-4%), 4.15 (ddd, 1H, J=7.0, 4.0, 2.0
Hz, H-2), 5.02 (d, 1H, J=7.0 Hz, H-1), 7.1 (m, 1H,
aromatic hydrogen), 7.25 (m, 1H, aromatic hydrogen),
7.36 (m, 1H, aromatic hydrogen), 7.57 (m, 1H, aro-
matic hydrogen); 13C NMR (CDCl3): l 26.2 (t), 27.6 (t),
64.3 (d), 69.1 (d), 126.4 (d), 128.1 (d), 128.5 (d), 130.2
(d), 133.9 (s), 135.5 (s); MS (EI) m/z: 184–182 (M+),
164 (M+−H2O), 146 (M+−Cl). Calcd for C10H11ClO: C,
65.93; H, 6.04. Found: C, 66.03; H, 6.05%.
4.3. (1R,2S)-2-p-Toluenesulphonyloxy-1-hydroxy-1,2,3,4-
tetrahydronaphthalene 6
Tosyl chloride (0.813 g, 4.28 mmol) in dry pyridine (2
mL) was added dropwise over 1 h, at 0°C under
stirring, to a solution of diol 1 (0.5 g, 3.4 mmol) in dry
pyridine (5 mL). The reaction was monitored by TLC
(Silica gel, eluting with n-hexane:ethyl acetate 6:4).
After stirring the reaction mixture for 3.5 h, ice-water
was added and the mixture extracted with ethyl acetate
(3×7 mL). The combined organic extracts were washed
with a 0.3N HCl till acid pH and then with a saturated
NaCl solution till neutral pH. The organic phase was
dried (Na2SO4) and the solvent removed under reduced
pressure. The crude material (0.632 g) was chro-
matographed (silica gel, eluting with n-hexane:ethyl
acetate, 6:4) and afforded the mono-tosylate 6 (0.29 g,
0.91 mmol, 30%), accompanied by 1-chloro-2-tosyl
4.6. (1R,2R)-1-Hydroxy-2-azido-1,2,3,4-tetrahydro-
naphthalene 7
Sodium azide (0.43 g, 6.6 mmol) was added to a
solution of the mono-tosylate 6 (1.05 g, 3.3 mmol) in
dry DMF (20 mL). The resulting suspension was heated
at 120°C in a pre-heated oil bath for 2 h, diluted with