S. Hanessian et al. / Tetrahedron 57 /2001) 6885±6900
6897
.400 MHz, CDCl3) d 7.39±7.26 .m, 7H), 7.07±7.03 .m,
1H), 6.98±6.87.m, 6H), 4.85 .AB, 2H, J11.2 Hz), 4.24
.dd, 1H, J6.9, 10.9 Hz), 4.04 .dd, 1H, J5.8, 10.9 Hz),
2.92±2.86 .m, 1H), 2.77 .d, 1H, J9.3 Hz), 1.44 .s, 9H);
13C NMR .100 MHz, CDCl3) d 166.3, 158.2, 154.5, 150.4,
136.3, 129.5, 128.8, 128.3, 128.1, 122.4, 120.6, 117.6,
115.7, 82.1, 74.9, 64.2, 47.1, 45.4, 27.9; LRMS .FAB,
NBA, m/z): 447.M 1), 392 .M2t-Bu); HRMS calcd for
C27H29NO5 .M1) 447.20456; found 447.20490.
J5.1, 12.0 Hz), 3.60 .dd, 1H, J7.0, 12.0 Hz), 2.68
.ddd, 1H, J5.5, 7.1, 9.1 Hz), 2.58 .ddd, 1H, J5.1, 7.0,
9.1 Hz), 2.49 .br. s, 1H); 13C NMR .100 MHz, CDCl3) d
154.4, 142.3, 137.9, 136.8, 128.6, 128.4, 128.1, 123.9,
121.5, 74.6, 65.6, 59.3, 47.4, 44.9; LRMS .TOF EI1, m/z,
%): 286 .100) .M1), 256 .87); HRMS calcd for C16H18O3N2
.M1) 286.13174; found 286.13146.
4.2.38. 1-Benzyloxy-2-0R)-0tert-butyl-dimethyl-silanyl-
oxymethyl)-3-0S)-04-phenoxy-phenoxymethyl)-aziridine
028a). To a solution of 27a .370 mg, 0.981 mmol) in CH2Cl2
.35 mL) at 08C, was added 2,6-lutidine .0.251 mL,
2.16 mmol) and TBSOTf .0.338 mL, 1.47mmol). After
stirring for 30 min, the mixture was diluted with CH2Cl2
.125 mL), successively washed with satd NaHCO3 and
satd NH4Cl, dried over Na2SO4, and concentrated in
vacuo. The residue was puri®ed by ¯ash chromatography
.hexanes/EtOAc, 49:1) to afford 28a .470 mg, 97%, yellow-
4.2.35. 1-Benzyloxy-3-0S)-0pyridin-3-yloxymethyl)-aziri-
dine-2-0R)-carboxylic acid tert-butyl ester 026b). Follow-
ing the same procedure described above, 25 .740 mg,
2.65 mmol), PPh3 .1.05 g, 4.0 mmol), 3-hydroxypyridine
.380 mg, 4.0 mmol) and DEAD .0.63 mL, 4.0 mmol)
afforded, after ¯ash chromatography .hexanes/EtOAc, 4:1
then 7:3), 26b .492 mg, 52%, yellowish oil); [a]D18.4 .c
0.7, CHCl3); Rf0.33 .hexanes/EtOAc, 1:1); IR .neat/NaCl)
1
1
3338.0, 1730.6 cm21; H NMR .400 MHz, CDCl3) d 8.32
ish oil); [a]D111.4 .c 0.8, CHCl3); H NMR .400 MHz,
.br. s, 1H), 8.22 .dd, 1H, J2.2, 3.5 Hz), 7.38±7.30 .m, 5H),
7.20 .m, 2H), 4.84 .AB, 2H, J11.5 Hz), 4.31 .dd, 1H,
J7.0, 10.8 Hz), 4.09 .dd, 1H, J5.6, 10.8 Hz), 2.88
.ddd, 1H, J5.6, 7.0, 9.3 Hz), 2.77 .d, 1H, J9.3 Hz),
1.44 .s, 9H); 13C NMR .100 MHz, CDCl3) d 166.2, 142.3,
138.2, 136.2, 128.7, 128.3, 128.0, 123.7, 120.9, 82.2, 74.9,
63.9, 46.7, 45.2, 27.8; LRMS .FAB, NBA, m/z, %): 356 .70)
.M1), 326 .65), 300 .15) .M2t-Bu), 272 .32), 204 .96), 176
.100); HRMS calcd for C20H24N2O4 .M1) 356.17361; found
356.17440.
CDCl3) d 7.46±7.29 .m, 7H), 7.10±7.06 .m, 1H), 7.03±6.88
.m, 6H), 4.84 .s, 2H), 4.05±3.96 .m, 2H), 3.75 .dd, 1H,
J7.1, 11.5 Hz), 3.69 .dd, 1H, J6.8, 11.5 Hz), 2.71±
2.66 .m, 1H), 2.60±2.54 .m, 1H), 0.96 .s, 9H), 0.14 .s,
3H), 0.13 .s, 3H); 13C NMR .100 MHz, CDCl3) d 158.3,
154.7, 150.4, 137.0, 129.5, 128.5, 128.3, 127.8, 122.4,
120.6, 117.6, 115.7, 74.3, 65.7, 60.5, 47.7, 45.1, 25.8,
18.2, 25.4, 25.5; LRMS .FAB, NBA, m/z): 492
.M1H1); HRMS calcd for C29H38O4NSi .M1H1)
492.25702; found 492.25630.
4.2.36. [1-Benzyloxy-3-0S)-04-phenoxy-phenoxymethyl)-
aziridin-2-0R)-yl]-methanol 027a). To a solution of 26a
.470 mg, 1.05 mmol) in CH2Cl2 .45 mL) at 2788C was
added DIBALH .2.8 mL, 4.20 mmol, 1.5 M solution in
toluene). After stirring for 30 min at 2788C and 30 min at
08C, 1 M HCl .30 mL) was slowly added and the solution
extracted with CH2Cl2, dried over Na2SO4, and concentrated
in vacuo. The residue was puri®ed by ¯ash chromatography
.hexanes/EtOAc, 3:2) to afford 27a .370 mg, 93%, colorless
oil); [a]D228.0 .c 1.2, CHCl3); 1H NMR .400 MHz,
CDCl3) d 7.40±7.29 .m, 7H), 7.09±7.05 .m, 1H), 7.01±
6.95 .m, 4H), 6.91±6.87.m, 2H), 4.82 .AB, 2H, J
11.5 Hz), 4.11 .dd, 1H, J7.2, 10.8 Hz), 3.88 .dd, 1H,
J6.2, 10.8 Hz), 3.66 .dd, 1H, J5.9, 12.2 Hz), 3.61 .dd,
1H, J7.0, 12.2 Hz), 2.70 .ddd, 1H, J6.3, 7.1, 9.1 Hz),
2.58 .ddd, 1H, J5.9, 6.9, 9.1 Hz), 2.06±1.98 .m, 1H);
13C NMR .100 MHz, CDCl3) d 158.2, 154.3, 150.6,
136.9, 129.5, 128.6, 128.0, 122.5, 120.6, 117.6, 115,7,
74.6, 65.7, 59.5, 47.3, 45.0; LRMS .FAB, NBA, m/z): 400
.M1Na1); HRMS calcd for C23H23O4NNa .M1Na1)
400.15247; found 400.15400.
4.2.39. 3-[1-Benzyloxy-3-0R)-0tert-butyl-dimethyl-silanyl-
oxymethyl)-aziridin-2-0S)-ylmethoxy]-pyridine
028b).
Following the same procedure described above, 27b
.220 mg, 0.77 mmol), 2,6-lutidine .0.197 mL, 1.69 mmol)
and TBSOTf .0.264 mL, 1.15 mmol) afforded, after ¯ash
chromatography .EtOAc), 28b .268 mg, 87%, colorless
oil); [a]D27.5 .c 2.1, CHCl3); Rf0.29 .hexanes/
1
EtOAc, 4:1); H NMR .400 MHz, CDCl3) d 8.34 .br. m,
1H), 8.23 .br. m, 1H), 7.38±7.33 .m, 5H), 7.22±7.19 .m,
2H), 4.79 .s, 2H), 4.08 .dd, 1H, J4.8, 10.8 Hz), 3.98 .dd,
1H, J7.5, 10.8 Hz), 3.74 .dd, 1H, J6.8, 10.6 Hz), 3.63
.dd, 1H, J5.8, 10.6 Hz), 2.64 .ddd, 1H, J4.8, 7.5,
9.0 Hz), 2.54 .ddd, 1H, J5.8, 6.8, 9.0 Hz), 0.91 .s, 9H),
0.09 .s, 3H), 0.08 .s, 3H); 13C NMR .100 MHz, CDCl3) d
154.7, 142.3, 138.1, 136.9, 128.6, 128.3, 127.9, 123.8,
121.3, 74.5, 65.7, 60.5, 47.7, 44.9, 25.8, 18.2, 25.3, 25.4;
LRMS .TOF EI1, m/z, %): 400 .1) .M1), 343 .100), 313
.17); HRMS calcd for C22H32O3N2Si .M1) 400.21282;
found 400.21973.
4.2.40. 2-0R)-0tert-Butyl-dimethyl-silanyloxymethyl)-3-
0S)-04-phenoxy-phenoxymethyl)-aziridine 029a). A mix-
ture of 28a .300 mg, 0.611 mmol) in EtOH .20 mL) was
stirred in presence of Pd/BaSO4 .300 mg, 5% w/w) under
H2 .1 atm) for 14 h. Filtration and ¯ash chromatography
.hexanes/EtOAc, 5:1) afforded 29a .210 mg, 89%, colorless
oil); [a]D15.5 .c 0.9, CHCl3); 1H NMR .400 MHz,
CDCl3) d 7.36±7.28 .m, 4H), 7.06±7.04 .m, 1H), 7.03±
6.88 .m, 4H), 4.05 .dd, 1H, J5.3, 10.3 Hz), 3.99 .dd,
1H, J6.8, 10.3 Hz), 3.83 .dd, 1H, J5.8, 11.2 Hz), 3.66
.dd, 1H, J6.1, 11.2 Hz), 2.58±2.54 .m, 1H), 2.46±2.41 .m,
1H), 1.92±1.80 .br. m, 1H), 0.92 .s, 9H), 0.09 .s, 3H), 0.08
.s, 3H); 13C NMR .100 MHz, CDCl3) d 158.3, 154.8, 150.2,
4.2.37. [1-Benzyloxy-3-0S)-0pyridin-3-yloxymethyl)-aziri-
din-2-0R)-yl]-methanol 027b). Following the same pro-
cedure described above, 26b .360 mg, 1.0 mmol) and
DIBAL±H .2.7mL, 4.0 mmol, 1.5 M solution in toluene)
afforded, after ¯ash chromatography .hexanes/EtOAc, 1:1
then 1:0), 27b .220 mg, 77%, colorless oil); [a]D218.1 .c
1.4, CHCl3); Rf0.21 .hexanes/EtOAc, 2:3); IR .neat/NaCl)
1
3381.1 cm21; H NMR .400 MHz, CDCl3) d 8.31 .dd, 1H,
J1.3, 2.0 Hz), 8.23 .dd, 1H, J2.5, 3.2 Hz), 7.38±7.33 .m,
5H), 7.22±7.19 .m, 2H), 4.82 .s, 2H), 4.08 .dd, 1H, J7.1,
10.6 Hz), 3.99 .dd, 1H, J5.5, 10.6 Hz), 3.69 .dd, 1H,