Synthesis of cis- and trans-2(S)-Amino-1-d-indane
J . Org. Chem., Vol. 62, No. 18, 1997 6209
EtOAc (2 mL) gave 6 (110 mg, 89%). Anal. Calcd for
C11H9DNOF3: C 57.39; H 4.80; N 6.08. Found C 57.50; H 5.00;
N 6.10. 1H-NMR (CD3CN), δ: 2.9 (dd; J ) 16.4, 5.5 Hz; 1 H);
3.3 (br dd, J ) 16.4, 7.6 Hz; 2 H); 4.6 (td, J ) 7.6, 5.5 Hz; 1
H); 7.1-7.3 (m; 4 H); 7.9 (br s; 1 H).
tr a n s-2-Tr iflu or oacetam ido-1-d-in dan e {7}. Under stan-
dard conditions, the reaction of trans-2-amino-1-d-indane (3)
(70 mg, 0.53 mmol) with (CF3CO)2NMe (116 µL, 0.8 mmol) in
EtOAc (1 mL) gave 7 (100 mg, 82%). Anal. Calcd for
C11H9DNOF3: C 57.39; H 4.80; N 6.08. Found C 57.70; H 4.61;
N 6.09. 1H-NMR (CD3CN), δ: 2.9 (dd; J ) 16.4, 5.5 Hz; 2 H);
3.3 (br dd, J ) 16.4, 7.6 Hz; 1 H); 4.6 (dt, J ) 7.6, 5.5 Hz; 1
H); 7.1-7.3 (m; 4 H); 7.9 (br s; 1 H).
3. cis-2-Azid o-1-(tosyloxy)in d a n e {9}. A solution of cis-
2-azido-1-indanol (8) (591 mg, 3.4 mmol) and NaH (122 mg, 4
mmol) in THF (40 mL) was strirred under Ar at -20 °C for 15
min. Then, TsCl (126 mg, 35 mmol) was slowly added in order
to maintain the temperature below -20 °C. The mixture was
stirred at -20 °C for 30 min, filtered through Celite, and
washed with ether. Evaporation of the solvents under reduced
pressure gave 9 (945 mg, 85%) as crude product which for
stability reasons was used without further purification. 1H-
NMR (CDCl3), δ: 2.5 (s; 3 H); 3.2 (d, J ) 6.8 Hz; 2 H); 4.1 (dt,
J ) 6.6, 5.2 Hz; 1 H); 5.9 (d, J ) 5.2 Hz; 1 H); 7.2-7.3 (m; 4
H); 7.4 (d, J ) 8.2 Hz; 2 H); 7.9 (d, J ) 8.2 Hz; 2 H). 13C-NMR
(CDCl3), δ: 21.6 (CH3); 34.8 (CH2); 62.2 (CH); 83.1 (CH); 125.0
(CH); 125.8 (CH); 127.6 (CH); 127.9 (CH); 129.8 (CH); 130.0
(CH); 136.3 (C); 140.1 (C); 133.7 (C); 145.1 (C).
4. cis-2-Azid o-1-(m esyloxy)in d a n e {10}. By the same
procedure described for compound 9, the reaction of cis-2-azido-
1-indanol (8) (464 mg, 2.65 mmol), 2.5 M nBuLi in hexanes
(1.16 mL, 2.9 mmol), and MsCl (205 mL, 2.6 mmol) in THF
(10 mL) gave compound 10 (518 mg, 85%) as crude product
which for stability reasons was used without further purifica-
tion. 1H-NMR (CDCl3), δ: 3.0 (s; 3 H); 3.1 (d, J ) 6.8 Hz; 2
H); 4.15 (dt, J ) 6.8, 5.1 Hz; 1 H); 5.9 (d, J ) 5.1 Hz; 1 H);
7.0-7.5 (m; 4 H). 13C-NMR (CDCl3), δ: 34.7 (CH2); 38.7 (CH3);
61.9 (CH); 82.8 (CH); 125.1 (CH); 126.0 (CH); 127.8 (CH); 130.6
(CH); 136.2 (C); 140.4 (C).
5. 2-Azid o-1-br om oin d a n es {11 a n d 12}. A solution of
cis-2-azido-1-indanol (8) (1.125 g, 6.4 mmol) and PBr3 (405 µL,
2.2 mmol) in CCl4 (200 mL) was strirred at rt until TLC (SiO2,
pentane) showed complete disappearance of compound 8. The
mixture is washed with brine and concentrated under reduced
pressure. Flash chromatography (SiO2, pentane) gave 11 (1
g, 66%) and 12 (426 mg, 28%). tr a n s-2-Azid o-1-br om oin -
d a n e {11}. Anal. Calcd for C9H8N3Br: C 45.40; H 3.39; N
17.65. Found C 42.97; H 3.63; N 17.12. 1H-NMR (CDCl3), δ:
2.9 (dd, J ) 16.4, 3.4 Hz; 1 H); 3.4 (dd, J ) 16.4, 6.3 Hz; 1 H);
4.5 (dt, J ) 3.4, 6.2 Hz; 1 H); 5.3 (d, J ) 3.4 Hz; 1 H); 7.1-7.5
(m; 4 H). 13C-NMR (CDCl3), δ: 36.5 (CH2); 54.6 (CH); 69.8
(CH); 125.0 (CH); 125.7 (CH); 128.0 (CH); 129.6 (CH); 139.8
(C); 140.5 (C). cis-2-Azid o-1-br om oin d a n e {12}. Anal.
Calcd for C9H8N3Br: C 45.40; H 3.39; N 17.65. Found C 43.57;
H 3.53; N 17.29. 1H-NMR (CDCl3), δ: 3.1 (d, J ) 7.9; 1 H);
4.05 (dt, J ) 7.9, 5.1 Hz; 1 H); 5.5 (d, J ) 5.1 Hz; 1 H); 7.1-
7.5 (m; 4 H). 13C-NMR (CDCl3), δ: 34.9 (CH2); 57.2 (CH); 63.4
(CH); 125.0 (CH); 125.2 (CH); 127.9 (CH); 129.7 (CH); 139.0
(C); 140.7 (C).
7. 2-(Tosyloxy)-2-d -in d a n e {17}. By the same procedure
described for compound 9, the reaction at -5 °C of 2-d-2-
indanol 16 (2.1 g, 15.5 mmol), NaH (520 mg, 17 mmol), and
TsCl (2.96 g, 15.5 mmol) in THF (100 mL) gave 17 (3.74 g,
83%) as crude product which was used without further
purification. 1H-NMR (CDCl3), δ: 2.4 (s; 3 H); 3.1 (d, J ) 6.5
Hz; 4 H); 7.1-7.3 (m; 4 H); 7.35 (d, J ) 8.2 Hz; 2 H); 7.8 (d, J
) 8.2 Hz; 2 H). 13C-NMR (CDCl3), δ: 21.5 (CH3); 39.5 (2 CH2);
82.1 (t, J C-D ) 23 Hz; CD); 124.4 (2 CH); 126.8 (2 CH); 133.9
(C); 138.9 (2 C); 144.7 (C).
8. 2-d -In d en e {18}. A solution of 2-(tosyloxy)-2-d-indane
17 (3.7 g, 13 mmol) and CH3ONa (700 mg, 13 mmol) in CH3OH
(50 mL) was stirred under Ar at 40 °C for 3 d. Flash
chromatography (SiO2, pentane) gave 18 (495 mg, 30%). Anal.
Calcd for C9H7D: C 92.27; H 7.73. Found C 92.50; H 7.71.
1H-NMR (CDCl3), δ: 3.4 (s; 2 H); 6.9 (s; 1 H); 7.2-7.5 (m; 4
H). 13C-NMR (CDCl3), δ: 39.0 (CH2); 121.0 (CH); 123.8 (CH);
124.6 (CH); 126.3 (CH); 132.0 (CH); 134.0 (t,J C-D ) 25 Hz; CD);
143.7 (C); 144.9 (C).
9. tr a n s-2-Br om o-2-d -1-in d a n ol {19}. A solution of 2-d-
indene 18 (46 µL, 0.4 mmol) and NBS (175 mg, 1 mmol) in
DMSO (1 mL) containing water (18 µL) was stirred at rt for 6
h. Water (2 mL) was added, and the mixture was extracted
with ether (3 × 5 mL). Organic layer was washed with brine
(2 × 5 mL), dried over Na2SO4, and concentrated under
reduced pressure. Flash chromatography (SiO2, CH2Cl2) gave
19 (80 mg, 95%). Anal. Calcd for C9H8DOBr: C 50.49; H 4.71.
Found C 51.11; H 4.63. 1H-NMR (CDCl3), δ: 2.6 (br s; 1 H);
3.2 (d, J ) 16.1 Hz; 1 H); 3.5 (d, J ) 16.1 Hz; 1 H); 5.3 (s; 1 H);
7.1-7.4 (m; 4 H). 13C-NMR (CDCl3), δ: 40.4 (CH2); 54.2 (t, J
) 24 Hz; CD); 83.4 (CH); 124.1 (CH); 124.6 (CH); 127.7 (CH);
129.0 (CH); 139.8 (C); 141.7 (C).
10. tr a n s-2-Azid o-2-d -1-in d a n ol {20}. A solution of
trans-2-bromo-2-d-1-indanol 19 (80 mg, 0.37 mmol) and NaN3
(29 mg, 0.44 mmol) in DMF (5 mL) was stirred at 80 °C for 3
h. Water (10 mL) was added, and the mixture was extracted
with ether (3 × 5 mL). Organic layer was washed with LiCl
saturated solution (2 × 5 mL), dried on Na2SO4, and concen-
trated under reduced pressure. Flash chromatography (SiO2,
CH3Cl2) gave 20 (63 mg, 98%). Anal. Calcd for C9H8DON3:
C 61.35; H 5.72; N 23.85. Found C 61.12; H 5.22; N 23.61.
1H-NMR (CDCl3), δ: 2.4 (br s; 1 H); 3.1 (s; 2 H); 5.1 (s; 1 H);
7.2-7.5 (m; 4 H). 13C-NMR (CDCl3), δ: 35.1 (CH2); 65.3 (t,
J C-D ) 24 Hz; CD); 76.4 (CH); 124.7 (CH); 125.1 (CH); 127.6
(CH); 129.0 (CH); 139.1 (C); 141.9 (C).
11. 2-Azid o-1-br om o-2-d -in d a n es {21 a n d 22}. By a
procedure analogous to the preparation of compounds 11 and
12, the reaction of cis-2-azido-2-d-1-indanol (20) (63 mg, 0.36
mmol) with PBr3 (32.5 µL, 0.18 mmol) in CCl4 (6 mL) gave 21
(54 mg, 64%) and 22 (21 mg, 25%). tr a n s-2-Azid o-1-br om o-
2-d -in d a n e {21}. Anal. Calcd for C9H7DN3Br: C 45.38; H
3.81; N 17.65. Found C 42.97; H 3.63; N 17.12. 1H-NMR
(CDCl3), δ: 2.9 (d, J ) 16.1 Hz; 1 H); 3.4 (d, J ) 16.1 Hz; 1 H);
5.3 (s; 1 H); 7.2-7.5 (m; 4 H). 13C-NMR (CDCl3), δ: 36.4 (CH2);
54.5 (CH); 69.9 (t, J C-D ) 24 Hz; CD); 125.1 (CH); 125.8 (CH);
128.1 (CH); 129.7 (CH); 139.8 (C); 140.5 (C). cis-2-Azid o-1-
br om o-2-d -in d a n e {22}. Anal. Calcd for C9H7DN3Br:
C
45.38; H 3.81; N 17.65. Found C 42.97; H 3.63; N 17.12. 1H-
NMR (CDCl3), δ: 3.1 (s; 2 H); 5.5 (s; 1 H); 5.3 (s; 1 H); 7.2-
7.45 (m; 4 H). 13C-NMR (CDCl3), δ: 35.0 (CH2); 57.1 (CH);
63.2 (t, J C-D ) 21 Hz; CD); 125.2 (CH); 125.4 (CH); 128.1 (CH);
129.9 (CH); 139.2 (C); 140.9 (C).
6. d -2-In d a n ol {16}. A solution of 2-indanone 15 (2.8 g,
21 mmol) and LiAlD4 (1.19 g, 28.6 mmol) in ether (150 mL)
was refluxed under Ar for 6 h. Water (20 mL) was carefully
added, and the mixture was stirred for 30 min. The suspen-
sion was filtered through Celite and concentrated under
reduced pressure. Flash chromatography (SiO2, CH3OH) gave
16 (2.1 g, 73%). Anal. Calcd for C9H9DO: C 79.97; H 8.19.
Ack n ow led gm en t. We are grateful to the French
Ministe`re des Affaires Etrange`res and Provence-Alpes-
Coˆte d’Azur country for the scholarship to two of us
(A.A.M. and C.B.). We thank Dr. Andreas Heumann
for helpful discussions.
1
Found C 80.05; H 8.10. H-NMR (CDCl3), δ: 1.7 (s; 1 H); 3.0
(d, J ) 16.3 Hz; 2 H); 3.3 (d, J ) 16.3 Hz; 2 H); 7.2-7.4 (m; 4
H). 13C-NMR (CDCl3), δ: 42.3 (2 CH2); 72.4 (t, J C-D ) 23 Hz;
CD); 124.8 (2 CH); 126.5 (2 CH); 140.9 (2 C).
J O970378O