8150 J. Am. Chem. Soc., Vol. 119, No. 35, 1997
Takayama et al.
alumina (4 mg) in H2O (0.5 mL) was hydrogenated under an atmos-
pheric pressure of hydrogen using a balloon with vigorous stirring for
3 h. The mixture was filtered through Celite, and the H2O was ly-
ophilized to give the title compound in quantitative yield. The face
selectivity was determined by the integration of the signal for 2 protons
of 9 at 4.24 ppm and the signal for 1 proton of 8 at 4.12 ppm.20
Enzymatic Acylation of Azido-Sugar Mixture 2, 3. To the azido-
sugar mixture (107 mg, 0.52 mmol) in THF (3 mL) was added vinyl
butyrate (1 mL) and porcine pancreatic lipase (PPL) (200 mg), and the
mixture was stirred at room temperature for 5 days. Filteration through
Celite followed by removal of the volatiles gave an oil which was
chromatographed (EtOAc/hexanes/MeOH ) 500/200/1) to yield dias-
tereomerically pure 4 (100 mg, 69%) and diastereomerically pure 5
(23 mg, 16%) as pale yellow oils.
4: 1H-NMR (400 MHz, CD3OD): δ 0.95 (t, 3H, J ) 7.4 Hz,
butyrate), 1.64 (sex, 2H, J ) 7.4 Hz, butyrate), 2.33 (t, 2H, J ) 7.4
Hz, butyrate), 3.34-3.44 (m, 1H, H-5), 3.41 (d, 1H, J ) 9.2 Hz, H-3),
3.55-3.65 (m, 2H, H-6ax, eq), 3.71 (t, 1H, J ) 9.4 Hz, H-4), 4.08 (d,
1H, J ) 11.3 Hz, H-1a), 4.11 (d, 1H, J ) 11.3 Hz, H-1b). 13C-NMR
(62.5 MHz, CD3OD): δ 13.9, 19.4, 36.8, 61.4, 63.4, 66.0, 72.9, 74.6,
97.9, 174.812. HRMS (FAB+) for C10H17N3O6 + Na+: calcd 298.1015,
found 298.1025.
5: 1H-NMR (400 MHz, CD3OD): δ 0.88 (t, 3H, J ) 7.4 Hz,
butyrate), 1.58 (sex, 2H, J ) 7.4 Hz, butyrate), 2.68 (t, 2H, J ) 7.4
Hz, butyrate), 3.56 (dd, 1H, J ) 1.5 and 12.5 Hz, H-6ax), 3.66 (d, 1H,
J ) 9.7 Hz, H-3), 3.74-3.75 (m, 1H, H-5), 3.94 (dd, 1H, J ) 3.9 and
9.8 Hz, H-4), 3.98 (d, 1H, J ) 12.5 Hz, H-6eq), 4.00 (d, 1H, J ) 11.2
Hz, H-1a), 4.07 (d, 1H, J ) 11.2 Hz, H-1b). 13C-NMR (62.5 MHz,
CD3OD): δ 13.9, 19.4, 36.9, 62.1, 64.2, 65.9, 69.8, 71.5, 98.3, 174.9.
HRMS (FAB+) for C10H17N3O6 + Na+: calcd 298.1015, found
298.1020.
5-Amino-5-deoxy-L-xylo-2-hexulopyranoside Hydrochloride (11).
A mixture of azido-sugar 2 (10 mg, 0.05 mmol) and 10% palladium-
carbon (3 mg) in 0.5 N HClaq (200 uL) was hydrogenated under an
atmospheric pressure of hydrogen, using a balloon, with vigorous
stirring for 10 min. The mixture was filtered through Celite, and the
H2O was lyophilized to give the title compound in quantitative yield
as a colorless solid. 1H-NMR (400 MHz, D2O): δ 3.27 (dt, 1H, J )
8.4 and 10.2 Hz, H-5), 3.51 (d, 1H, J ) 11.8 Hz, H-1a), 3.55 (d, 1H,
J ) 9.3 Hz, H-3), 3.71 (d, 1H, J ) 11.8 Hz, H-1b), 3.86 (dd, 1H, J )
9.4 and 10.3 Hz, H-4), 3.90 (d, 2H, J ) 8.4 Hz, H-6ax, eq). 13C-NMR
(100 MHz, D2O): δ 51.8, 58.8, 63.6, 70.3, 70.9, 98.5. HRMS (FAB+)
for C6H13N1O5 + H+: calcd 180.0872, found 180.0879.
2,N-Dehydro-2,5-dideoxy-2,5-imino-L-gulo-hexitol (13). Addition
of 7 µL of 10 N NaOD to the NMR tube of the D2O solution of 11
resulted in immediate formation of the cyclic imine 13. 1H-NMR (500
MHz, D2O): δ 3.81 (dd, 1H, J ) 4.0 and 9.2 Hz, H-6a), 3.86 (dd, 1H,
J ) 4.0 and 9.2 Hz, H-6b), 4.01-4.08 (m, 1H, H-5), 4.24 (t, 1H, J )
3.6 Hz, H-4), 4.42 (s, 2H, H-1a,b), 4.61 (d, 1H, J ) 3.6 Hz, H-3). 13C-
NMR (125 MHz, D2O): δ 60.4, 60.6, 72.5, 78.8, 83.0, 182.2.
5-Amino-5-deoxy-D-arabino-2-hexulopyranoside Hydrochloride
(15). A mixture of azido-sugar 3 (9 mg, 0.044 mmol) and 10%
palladium-carbon (3 mg) in 1 N HClaq (100 µL) was hydrogenated
under an atmospheric pressure of hydrogen, using a balloon, with
vigorous stirring for 10 min. The mixture was filtered through Celite,
and the H2O was lyophilized to give the title compound in quantitative
yield as a colorless solid. 1H-NMR (400 MHz, D2O): δ 3.51 (d, 1H,
J ) 9.6 Hz, H-1a), 3.62 (d, 1H, J ) 8.4 Hz, H-3), 3.63-3.66 (m, 1H,
H-5), 3.69 (d, 1H, J ) 9.6 Hz, H-1b), 3.75 (d, 1H, J ) 11.2 Hz, H-6ax),
4.12 (dd, 1H, J ) 4.0 and 8.4 Hz, H-4), 4.17 (d, 1H, J ) 11.2 Hz,
H-6eq). 13C-NMR (100 MHz, D2O): δ 52.4, 58.5, 63.4, 66.4, 67.2,
98.0. HRMS (FAB+) for C6H13N1O5 + H+: calcd 180.0872, found
180.0877.
10% palladium-carbon (3 mg) in 0.5 N HClaq (140 µL) was
hydrogenated under an atmospheric pressure of hydrogen, using a
balloon, with vigorous stirring for 5 min. The mixture was filtered
through Celite, and the H2O was lyophilized to give the title compound
in quantitative yield as a colorless solid. 1H-NMR (500 MHz, D2O):
δ 0.86 (t, 3H, J ) 7.5 Hz, butyrate), 1.57 (sex, 2H, J ) 7.5 Hz,
butyrate), 2.36 (t, 2H, J ) 7.5 Hz, butyrate), 3.25 (dt, 1H, J ) 6.5 and
10.5 Hz, H-5), 3.50 (d, 1H, J ) 9.5 Hz, H-3), 3.85 (dd, 1H, J ) 9.5
and 10.5 Hz, H-4), 3.86 (dd, 1H, J ) 6.5 and 11.2 Hz, H-6ax), 3.89 (t,
1H, J ) 11.2 Hz, H-6eq), 4.12 (d, 1H, J ) 11.5 Hz, H-1a), 4.20 (d, 1H,
J ) 11.5 Hz, H-1b). 13C-NMR (125 MHz, D2O): δ 13.6, 18.7, 36.3,
52.0, 59.2, 65.5, 70.3, 71.9, 97.5, 176.5. HRMS (FAB+) for C10H19N1O6
+ H+: calcd 250.1290, found 250.1286.
1-Butyroyl 2,N-Dehydro-2,5-dideoxy-2,5-imino-L-gulo-hexitol (12).
Addition of 7 µL of 10 N NaOD to the NMR tube of the D2O solution
of 10 resulted in immediate formation of the cyclic imine 12. 1H-
NMR (500 MHz, D2O): δ 0.85 (t, 3H, J ) 7.5 Hz, butyrate), 1.50
(sex, 2H, J ) 7.5 Hz, butyrate), 2.11 (t, 2H, J ) 7.5 Hz, butyrate),
3.81 (dd, 1H, J ) 5.0 and 11.5 Hz, H-6a), 3.85 (dd, 1H, J ) 5.0 and
11.5 Hz, H-6b), 4.03-4.08 (m, 1H, H-5), 4.23 (dd, 1H, J ) 4.0 and
6.0 Hz, H-4), 4.41 (s, 2H, H-1a,b), 4.59 (d, 1H, J ) 4.0 Hz, H-3). 13C-
NMR (125 MHz, D2O): δ 14.0, 20.1, 40.4, 60.4, 60.7, 72.6, 78.9, 83.1,
182.3, 185.0.
1-Butyroyl 5-Amino-5-deoxy-D-arabino-2-hexulopyranoside Hy-
drochloride (14). A mixture of azido-sugar 5 (8.4 mg, 0.030 mmol)
and 10% palladium-carbon (3 mg) in 0.33 N HClaq (186 µL) was
hydrogenated under an atmospheric pressure of hydrogen, using a
balloon, with vigorous stirring for 5 min. The mixture was filtered
through Celite, and the H2O was lyophilized to give the title com-
pound in quantitative yield as a colorless solid. 1H-NMR (500
MHz, D2O): δ 0.86 (t, 3H, J ) 7.5 Hz, butyrate), 1.56 (sex, 2H,
J ) 7.5 Hz, butyrate), 2.38 (t, 2H, J ) 7.5 Hz, butyrate), 3.60 (d, 1H,
J ) 10.0 Hz, H-3), 3.65-3.68 (m, 1H, H-5), 3.76 (dd, 1H, J ) 1.5
and 14.0 Hz, H-6ax), 4.14 (dd, 1H, J ) 5.0 and 10.0 Hz, H-4), 4.19
(dd, 1H, J ) 2.0 and 14.0 Hz, H-6eq), 4.19 (s, 2H, 1-Ha,b). 13C-NMR
(125 MHz, D2O): δ 13.6, 18.6, 36.3, 53.0, 59.5, 66.4, 66.8, 68.9, 97.6,
177.1. HRMS (FAB+) for C10H17N1O5 + H+: calcd 250.1291, found
250.1295.
1-Butyroyl 2,N-Dehydro-2,5-dideoxy-2,5-imino-D-gluco-hexitol
(16). Addition of 7 µL of 10 N NaOD to the NMR tube of the D2O
solution of 14 resulted in immediate formation of the cyclic imine 16.
1H-NMR (500 MHz, D2O): δ 0.86 (t, 3H, J ) 7.5 Hz, butyrate), 1.52
(sex, 2H, J ) 7.5 Hz, butyrate), 2.12 (t, 2H, J ) 7.5 Hz, butyrate),
3.69-3.75 (m, 2H, H-6a,b), 3.77-3.81 (m, 1H, H-5), 3.98 (t, 1H, J )
4.5 Hz, H-4), 4.40 (s, 2H, H-1a,b), 4.55 (d, 1H, J ) 4.5 Hz, H-3). 13C-
NMR (125 MHz, D2O): δ 14.1, 20.2, 40.4, 60.4, 62.2, 76.1, 80.5, 83.6,
182.5, 185.0.
6-Amino-6,7-dideoxy-L-galacto-2-septulofuranoside Hydrochlo-
ride (18). The title compound was obtained in a manner analogous to
the procedure for compound 11. 1H-NMR (500 MHz, D2O): δ 1.16
(d, 3H, J ) 6.8 Hz, H-7), 3.31 (dq, 1H, J ) 8.8 and 6.9 Hz, H-6), 3.37
(d, 1H, JAB ) 12.2 Hz, H-1), 3.40 (d, 1H, JAB ) 12.2 Hz, H-1), 3.54
(dd, 1H, J ) 8.9 and 6.8 Hz, H-5), 3.91 (d, 1H, J ) 7.9 Hz, H-3), 3.99
(dd, 1H, J ) 7.8 and 6.8 Hz, H-4). 13C-NMR (125 MHz, D2O): δ
14.64, 52.65, 63.00, 76.58, 77.40, 81.46, 102.92. HRMS (FAB+) for
C7H15N1O5 + H+: calcd 194.1028, found 194.1022.
2,N-Dehydro-2,6-imino-2,6,7-trideoxy-L-glycero-D-manno-hepti-
tol (19). Addition of 10 N NaOD to the NMR tube of the D2O solution
of 18 resulted in immediate formation of the cyclic imine 19. 1H-
NMR (500 MHz, D2O): δ 0.92 (d, 3H, J ) 6.6 Hz, H-7), 3.06 (q, 1H,
J ) 6.7 Hz, H-6), 3.35 (d, 1H, JAB ) 11.5 Hz, H-1), 3.43 (d, 1H, JAB
) 11.4 Hz, H-1), 3.49 (d, 1H, J ) 10.0 Hz, H-3), 3.59 (m, 1H, H-5),
3.63 (dd, 1H, J ) 10.0 and 3.2 Hz, H-4). 13C-NMR (125 MHz, D2O):
δ 17.04, 47.08, 65.93, 69.82, 72.31, 73.08, 171.15.
2-Cyano-2,6-imino-2,6,7-trideoxy-L-glycero-D-manno-heptitol (23).
To the amine hydrochloride 18 (243 mg, 1.06 mmol) was added dioxane
(8 mL) under Ar, followed by a solution of KCN (104 mg, 1.59 mmol)
in water (1.6 mL). The resulting mixture was then stirred at 20 °C for
1 week. The volatiles were evaporated, and the residue chromato-
graphed using a mixture of CH3CN and H2O (10:1, Rf ) 0.5) to yield
the desired compound as a pale yellow solid (166 mg, 77%): 1H-NMR
(400 MHz, D2O): δ 0.95 (d, 3H, J ) 6.6 Hz, H-7), 2.93 (dq, 1H, J )
2,N-Dehydro-2,5-dideoxy-2,5-imino-D-gluco-hexitol 17. Addition
of 7 µL of 10 N NaOD to the NMR tube of the D2O solution of 15
resulted in immediate formation of the cyclic imine 17. 1H-NMR (500
MHz, D2O): δ 3.70-3.75 (m, 2H, H-6a,b), 3.79-3.82 (m, 1H, H-5),
4.00 (t, 1H, J ) 4.5 Hz, H-4), 4.40 (s, 2H, H-1a,b), 4.56 (d, 1H, J ) 4.5
Hz, H-3). 13C-NMR (125 MHz, D2O): δ 60.3, 62.2, 75.9, 80.4, 83.4,
182.0.
1-Butyroyl 5-Amino-5-deoxy-L-xylo-2-hexulopyranoside Hydro-
chloride (10). A mixture of azido-sugar 4 (7.5 mg, 0.027 mmol) and