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1H NMR, δ: 7.50–7.10 (m; 4H), 4.80 (d, J 5.5 Hz; 1H), 4.15 (ddd, J 7.6, 6.6 and 5.5 Hz; 1H), 3.35
(dd, J 16.3 and 7.6 Hz; 1H), 2.95 (dd, J 16.3 and 6.6 Hz; 1H). 13C NMR, δ: 140.0 (C), 139 (C), 129.4
(CH), 127.6 (CH), 125.0 (CH), 124.4 (CH), 70.1 (CH), 67.5 (CH), 36 (CH2). HPLC: hexane:isopropanol
(99.75:0.25), 1 mL/min; retention time: 7 min for (1S,2S)-4 and 16 min for (1R,2R)-4.
4.3. trans-1,2-Diaminoindane 5
A solution of 4 (500 mg, 2.5 mmol) in absolute EtOH (40 mL) was hydrogenated with H2 in the
presence of 10% Pd/C (50 mg) at rt for 12 h. The mixture was centrifuged and concentrated under
reduced pressure to give 5 (370 mg, 99%) as the crude product. 1H NMR, δ: 7.40–7.20 (m; 4H), 3.75 (d,
J 7.2 Hz; 1H), 3.20 (m; 2H), 2.60 (dd, J 13 and 6.5 Hz; 1H), 1.80 (br. s; 4H). 13C NMR, δ: 144.6 (C),
139.5 (C), 127.2 (CH), 126.5 (CH), 124.2 (CH), 122.8 (CH), 64.3 (CH), 63.4 (CH), 38.8 (CH2).
4.4. trans-[N,N0-Di(3,5-di-tert-butyl-2-hydroxy-benzylideneamino)-indane] 6
3,5-di-tert-Butyl-2-hydroxy-benzaldehyde (0.47 g, 2 mmol) was added as a solid to a solution of 5
(0.2 g, 1 mmol) in absolute EtOH (10 mL). The mixture was heated to reflux for 1 h and then water was
added (3 mL). The resulting yellow solid was collected by filtration to give 6 (0.55 g, 95%). C39H52N2O2
(580.4): calcd C 80.63, H 9.03, N 4.83; found C 79.39, H 8.50, N 4.18. 1H NMR, δ: 13.55 (s; 1H), 13.50
(s; 1H), 8.50 (s; 1H), 8.45 (s; 1H), 7.40–7.00 (m; 8H), 4.90 (d, J 7.3 Hz; 1H), 4.30 (dt, J 8.6 and 7.3
Hz; 1H), 3.35 (d, J 8.6 Hz; 2H), 1.45 (s; 9H), 1.25 (s; 9H). 13C NMR, δ 168.0 (CH), 167.2 (CH), 158.1
(C), 142.2 (C), 140.4 (C), 140.3 (C), 136.7 (C), 128.3 (CH), 127.9 (CH), 127.3 (CH), 127.2 (CH), 126.6
(CH), 126.5 (CH), 124.8 (CH), 124.2 (CH), 117.8 (C), 79.7 (CH), 78.0 (CH), 39.1 (CH2), 35.1 (C), 34.2
(C), 31.5 (CH3), 29.5 (CH3). HPLC: hexane:isopropanol (99.75:0.25), 1 mL/min; retention time: 2.9 min
for (1S,2S)-6 and 3.7 min for (1R,2R)-6.
4.5. Lipase catalyzed transesterification of (ꢀ)-trans-1-azido-2-indanol 7
A suspension of (ꢀ)-7 (4.28 g, 24 mmol), vinyl acetate (11 g, 123 mmol) and lipase 237.87 (1.73
g) in hexane:ether (120:80 mL) was stirred at 40°C for 3 h. The suspension was filtered and dried over
Na2SO4. Concentration under reduced pressure followed by flash chromatography (SiO2, CH2Cl2) gave
(1R,2R)-8 (2.33 g, 44%, 97% ee) and (1S,2S)-7 (1.59 g, 37%, 98% ee).
(+)-(1S,2S)-trans-1-Azido-2-indanol (1S,2S)-7: Clear yellow oil. [α]25=+74.2 (c 41, CHCl3).
D
1
C9H9N3O (175.07): calcd C 61.69, H 5.18, N 23.0; found C 60.58, H 5.12, N 23.96. H NMR, δ:
7.40–7.10 (m; 4H), 4.65 (d, J 5.1 Hz; 1H), 4.45 (ddd, J 6.6, 5.8 and 5.1 Hz; 1H), 3.25 (dd, J 16.2
and 6.6 Hz; 1H), 2.86 (dd, J 16.2 and 5.8 Hz; 1H), 2.08 (br. s; 1H). 13C NMR, δ: 139.8 (C), 137.9
(C), 129.2 (CH), 127.5 (CH), 125.4 (CH), 124.7 (CH), 78.7 (CH), 71.9 (CH), 39.0 (CH2). HPLC:
hexane:isopropanol (98:2), 1 mL/min; retention time: 19 min for (1S,2S)-7 and 24 min for (1R,2R)-7.
(−)-(1R,2R)-trans-1-Azido-2-acetoxyindane (1R,2R)-8: Clear yellow oil. [α]25=−81.6 (c 46, CHCl3).
D
1
C11H11N3O2 (217.08): calcd C 60.81, H 5.11, N 19.35; found C 60.69, H 5.06, N 20.12. H NMR, δ:
7.40–7.10 (m; 4H), 5.32 (ddd, J 6.9, 4.6 and 4.1 Hz; 1H), 4.85 (d, J 4.1 Hz; 1H), 3.50 (dd, J 16.8 and 6.9
Hz; 1H), 2.85 (dd, J 16.8 and 4.8 Hz; 1H), 2.05 (s; 3H). 13C NMR, δ: 170.7 (C), 139.8 (C), 137.4 (C),
129.4 (CH), 127.5 (CH), 125.2 (CH), 124.7 (CH), 79.4 (CH), 69.4 (CH), 36.8 (CH2), 21.0 (CH3). HPLC:
hexane:isopropanol (98:2), 1 mL/min; retention times: 5 min for (1S,2S)-8 and 7 min for (1R,2R)-8.