(0.80 mL, 2.0 equiv., 5.71 mmol), tosyl chloride (545 mg, 1.0
equiv., 2.86 mmol) and DMAP (35 mg, 0.10 equiv., 0.29 mmol).
The mixture was warmed to rt and stirred for 16 h. The solution
was then diluted with dichloromethane (20 mL) and washed
successively with 5% v/v aqueous hydrochloric acid solution
(10 mL), 5% w/v aqueous sodium hydrogen carbonate solution
(10 mL) and brine (10 mL). The organic extract was then dried
(MgSO4), concentrated in vacuo and purified by flash column
chromatography (10% v/v ethyl acetate–petrol) to afford ( )-29
as a white solid (691 mg, 74%); mp 71–72 ЊC (found C 58.15;
H 4.56; N 12.85. calc for C16H15N3O3S C 58.36; H 4.56;
N 12.77%); νmax(Nujol)/cmϪ1 2108, 1596, 1372, 1181; δH (250
MHz, CDCl3) 7.86 (2H, d, J 8.6, SO2(C6H4)CH3), 7.37 (2H, d,
J 8.6, SO2(C6H4)CH3), 7.35–7.24 (3H, m, aryl H), 7.22–7.18
(1H, m, aryl H), 4.98–4.89 (2H, m, 2 × CH), 3.36 (1H, dd,
J 16.8, 6.7, CHH), 3.05 (1H, dd, J 16.8, 5.5, CHH ), 2.47 (1H, s,
CH3); δC (63 MHz, CDCl3) 145.2, 138.5, 136.5, 133.2, 130.0,
129.6, 127.9, 127.8, 125.1, 124.6, 85.2, 69.3, 36.9, 21.6; MS
m/z (CI) 347 ([M ϩ NH4]ϩ, 42%), 302 (33%), 287 (73%), 155
(37%), 129 (100%), 91 (57%), 65 (17%).
afford ( )-31 as a white solid (186 mg, 41%); mp 165–166 ЊC;
νmax(Nujol)/cmϪ1 3242, 1596, 1359, 1149, 1091, 995; δH (250
MHz, CDCl3) 7.78 (4H, d, J 8.4, aryl H), 7.39–7.12 (7H, m, aryl
H), 6.99 (1H, d, J 7.0, aryl H), 4.92 (1H, m, CHOTs), 4.80 (1H,
m, CHNTs), 4.64 (1H, d, J 7.0, NH), 3.22 (1H, dd, J 16.3, 6.6,
CHH), 2.95 (1H, dd, J 16.3, 5.1, CHH), 2.47 (6H, s, 2 × CH3);
δC (63 MHz, CDCl3) 145.0, 143.7, 138.4, 137.8, 137.1, 133.1,
129.9, 129.8, 129.3, 128.1, 127.8, 127.3, 125.0, 124.5, 85.4 (CH),
62.9 (CH), 36.4 (CH2), 21.7 (CH3), 21.6 (CH3); MS m/z (CI) 475
([M ϩ NH4]ϩ, 3%), 406 (2%), 347 (6%), 303 (10%), 286 (100%),
22 (7%). HRMS: calc for C23H27N2O5S2: 475.1361, ([M ϩ
NH4]ϩ) found 475.1361.
( )-trans-1-Aminoindan-2-ol 1710
To a stirred solution of tin() chloride dihydrate (387 mg,
3.0 equiv., 1.71 mmol) in THF (5 mL)–water (3 mL) at 0 ЊC was
added a solution of ( )-19 (100 mg, 1.0 equiv., 0.57 mmol)
in THF (3 mL). The mixture was warmed to rt and stirred
for 18 h. The solvent was then removed in vacuo and the residue
dissolved in dilute hydrochloric acid (5 mL, 2 M). The acidic
aqueous phase was then extracted with ether (2 × 15 mL). The
combined ethereal extracts were discarded and the aqueous
layer basified to pH 14 by the dropwise addition of 2 M
aqueous sodium hydroxide solution at 0 ЊC. The aqueous layer
was extracted with ethyl acetate (5 × 25 mL). The combined
organic extracts were dried (MgSO4) and concentrated in vacuo
to afford ( )-17 as a beige solid (70 mg, 82%).
(1S,2S)-(؉)-trans-1-Azido-2-( p-tolylsulfonyloxy)indane 29
This compound was prepared according to the procedure
employed for ( )-29 using (1S,2S)-19 (91% ee) (2.00 g, 11.43
mmol), tosyl chloride (2.18 g, 1.0 equiv., 11.43 mmol), triethyl-
amine (3.20 mL, 2.0 equiv., 22.86 mmol) and DMAP (139 mg,
0.10 equiv., 1.14 mmol) in dichloromethane (15 mL) for 17 h at
rt. The product was a light beige solid (1S,2S)-29 (3.02 g, 80%)
and determined to be of 91% ee by HPLC analysis (Chiralcel
OD, propan-2-ol–hexane = 5 : 95 (0.5 mL minϪ1), (1S,2S) iso-
mer 18.8 min, (1R,2R) isomer 24.8 min); [α]2D8 ϩ46.1 (c 0.80,
CHCl3).
( )-N-Tosyl-1,1a,6,6a-tetrahydroindeno[1,2-b]azirene 2616
To a stirred solution of ( )-31 (150 mg, 0.33 mmol) in THF
(5 mL) at 0 ЊC was added sodium hydride (26 mg, 2.0 equiv.,
0.66 mmol, 60%). The mixture was warmed to rt and stirred
for 22 h. To the suspension was added water (10 mL) and the
separated aqueous layer was extracted with ethyl acetate (3 ×
15 mL). The organic extract was washed with brine (15 mL),
dried (MgSO4) and concentrated in vacuo. The crude product
was purified by flash column chromatography (15% v/v ethyl
acetate–petrol) to afford ( )-26 as a white solid (58 mg, 64%);
δH (250 MHz, CDCl3) 7.83 (2H, d, J 8.2, aryl H), 7.40 (1H, d,
J 6.7, aryl H), 7.32 (2H, d, J 8.2, aryl H), 7.29–7.14 (3H, m, aryl
H), 4.30 (1H, d, J 5.2, CH(1)NTs), 3.92–3.88 (1H, m,
CH(2)NTs), 3.14 (2H, obs br s, CH2), 2.44 (3H, s, CH3).
( )-trans-1-Amino-2-( p-tolylsulfonyloxy)indane 30
To a stirred solution of tin() chloride dihydrate (1.32 g,
3.0 equiv., 5.84 mmol) in THF (20 mL)–water (10 mL) at 0 ЊC
was added a solution of ( )-29 (640 mg, 1.0 equiv., 1.95 mmol)
in THF (10 mL). The mixture was warmed to rt and stirred
for 16 h. The solution was basified to pH 14 by the dropwise
addition of 2 M aqueous sodium hydroxide solution at 0 ЊC.
The aqueous layer was extracted with ethyl acetate (3 × 60 mL).
The combined organic extracts were washed with brine (50
mL), dried (MgSO4) and concentrated in vacuo. The crude
product was purified by flash column chromatography (60%
v/v ethyl acetate–petrol) to afford ( )-30 as a white solid
(494 mg, 84%); mp 202–204 ЊC (decomp.); νmax(Nujol)/cmϪ1
3448, 1598, 1528, 1195, 1126; δH (250 MHz, CDCl3) 7.86 (2H,
d, J 8.0, SO2(C6H4)CH3), 7.37 (2H, d, J 8.0, SO2(C6H4)CH3),
7.33–7.02 (4H, m, aryl H), 4.74 (1H, obs q, J 7.0, CHOTs), 4.46
(1H, d, J 6.4, CHNH2), 3.18 (1H, dd, J 16.0, 7.6, CHH), 2.94
(1H, dd, J 16.0, 7.6, CHH ), 2.33 (2H, br s, NH2); δC (63 MHz,
DMSO-d6) 145.6, 139.5, 135.2, 132.6, 130.5, 130.0, 128.3,
127.8, 125.6, 125.2, 83.3, 59.2, 36.6, 20.9; MS m/z (CI) 304
([M ϩ H]ϩ, 2%), 244 (4%), 149 (7%), 132 (100%), 116 (2%), 108
(5%); HRMS: calc for C16H18NO3S 304.1007, ([M ϩ H]ϩ) found
304.1007.
( )-trans-1-Azido-2-( p-tolylsulfonylamino)indane 32
A mixture of ( )-26 (55 mg, 0.19 mmol) and sodium azide
(20 mg, 1.60 equiv., 0.31 mmol) in 80% v/v aqueous ethanol
(4 mL) was refluxed for 7 h. Following cooling, brine (10 mL)
was added and the separated aqueous layer was extracted
with ethyl acetate (3 × 15 mL). The combined organic extracts
were washed with brine (15 mL), dried (MgSO4) and concen-
trated in vacuo. The crude product was purified by flash column
chromatography (20% v/v ethyl acetate–petrol) to afford ( )-32
as a gummy beige solid (61 mg, 95%); mp 71–73 ЊC; νmax(Nujol)/
cmϪ1 3259, 2097, 1322, 1161, 1087; δH (250 MHz, CDCl3)
7.81 (2H, d, J 8.0, SO2(C6H4)CH3), 7.32 (2H, d, J 8.0, SO2-
(C6H4)CH3), 7.29–7.17 (3H, m, aryl H), 7.15 (1H, m, aryl H),
5.72 (1H, d, J 7.9), 4.66 (1H, d, J 6.1), 3.86 (1H, obs quintet,
J 7.1, CHNHTs), 3.16 (1H, dd, J 16.6, 7.6, CHH), 2.71 (1H, dd,
J 16.0, 7.0, CHH ), 2.44 (3H, s, CH3); δC (63 MHz, CDCl3)
143.8 (C), 139.2 (C), 137.7 (C), 137.0 (C), 129.8, 129.2, 127.5,
127.1, 125.0, 124.4, 70.1 (CH), 60.5 (CH), 37.4 (CH2), 21.5
(CH3); MS m/z (CI) 346 ([M ϩ NH4]ϩ, 4%), 318 (4%),
301 (23%), 189 (7%), 145 (100%), 91 (10%); HRMS: calc for
C16H20N5O2S: 346.1338, ([M ϩ NH4]ϩ) found 346.1338.
( )-trans-N,O-Bis( p-tolylsulfonyl)-1-aminoindan-2-ol 31
To a stirred solution of ( )-30 (300 mg, 0.99 mmol) in dichloro-
methane (10 mL) at 0 ЊC were added sequentially triethylamine
(0.28 mL, 2.0 equiv., 1.98 mmol), tosyl chloride (189 mg,
1.0 equiv., 0.99 mmol) and DMAP (12 mg, 0.10 equiv.,
0.01 mmol). The mixture was warmed to rt and stirred for 16 h.
The solution was then diluted with dichloromethane (10 mL)
and washed successively with 5% v/v aqueous hydrochloric
acid solution (10 mL), 5% w/v aqueous sodium bicarbonate
solution (10 mL) and brine (10 mL). The organic extract was
then dried (MgSO4), concentrated in vacuo and purified by flash
column chromatography (10 20% v/v ethyl acetate–petrol) to
( )-cis-1,2-Diazidoindane 34
A mixture of ( )-29 (300 mg, 0.91 mmol) and sodium azide
(89 mg, 1.50 equiv., 1.37 mmol) in DMF (3 mL) was heated at
424
J. Chem. Soc., Perkin Trans. 1, 2002, 416–427