(1H, m, H-4), 4.27 (1H, dd, J6,6Ј 11.1, J6,5 7.0, H-6), 4.15
(1H, dd, J6Ј,6 11.1, J6Ј,5 4.1, H-6Ј), 4.00 (1H, m, H-1), 3.27
(1H, dt, J5,6Ј 4.1, J5,6 = J5,4 7.0, H-5), 2.98 (1H, dd, J 17.0, 9.1,
CHHCOPh), 2.56 (1H, dd, J 17.0, 4.4, CHHCOPh), 1.95 (1H,
br s, NH), 1.77 (6H, s, 2 × CH3); δC (100 MHz; C6D6) 197.7
dichloromethane (3 × 10 cm3). The combined organic layers
were dried over MgSO4, filtered and concentrated in vacuo. The
residue was redissolved in dichloromethane (2 cm3) at room
temperature and piperidine (250 µl, 2.52 mmol) added. After
stirring for 1 h, the solution was concentrated in vacuo. Column
chromatography (ethyl acetate–light petroleum; 1 : 4) provided
(C᎐O), 169.9 (C᎐O), 169.7 (C᎐O), 137.2 (ArC), 134.2 (C-2),
᎐
᎐
᎐
1
132.7 (ArCH), 128.4 (ArCH), 128.0 (ArCH), 125.1 (C-3),
66.9 (C-4), 63.4 (C-6), 51.9 (C-5), 47.6 (C-1), 42.5 (CH2), 20.4
(CH3), 20.1 (CH3); m/z (CI) 332 (M ϩ Hϩ), 212, 154, 152.
HRMS (ESϩ); calcd for C18H22NO5 (M ϩ Hϩ) 332.1498, found
332.1502.
a 1 : 1.4 mixture of 12 and 11 respectively as judged by H
NMR spectroscopy (59 mg, 80%). Partial separation of the two
diastereomers was carried out using MPLC on a Merck Lobar
Lichroprep Si60 column to give 12 (20 mg, 27%) as a colourless
oil; [α]2D5 ϩ191 (c 1.0, CHCl3); νmax (neat)/cmϪ1 3458 (NH), 3343
(NH), 3035, 2963, 2929, 2876, 1743 (C᎐O), 1233; δ (400 MHz;
᎐
H
ꢀ-(1,5-Anhydro-2,3-dideoxy-4,6-di-O-acetyl-1,5-imino-ꢀ-D-
erythro-hex-2-eno-pyranosyl)methylcyclohexene 9d and ꢁ-(1,5-
anhydro-2,3-dideoxy-4,6-di-O-acetyl-1,5-imino-ꢁ-D-erythro-hex-
2-eno-pyranosyl)methylcyclohexene 10d
CDCl3) 6.02 (1H, dd, J2,3 10.2, J 3.4, H-2), 5.84 (1H, ddd, J3,2
10.2, J3,4 4.5, 2.0, H-3), 5.13 (1H, m, H-4), 4.14 (1H, dd, J6,6Ј
11.1, J6,5 5.9, H-6), 4.06 (1H, dd, J6Ј,6 11.1, J6Ј,5 8.0, H-6Ј), 3.36
(1H, ddd, J5,6Ј 8.0, J5,6 5.9, J5,4 3.5, H-5), 3.30–3.25 (1H, m, H-
1), 2.07 (3H, s, CH3), 2.06 (3H, s, CH3), 1.75 (1H, br s, NH),
1.55–1.43 (2H, m, CH2CH3), 0.97 (3H, t, J 7.4, CH2CH3); δC
To a stirred solution of 2 (100 mg, 0.203 mmol) in dichloro-
methane (2 cm3) at room temperature was added methyl-
enecyclohexane (29 µl, 0.241 mmol), followed by tin ()
bromide (133 mg, 0.31 mmol) in dichloromethane (2 cm3). The
resulting solution was stirred for 5 min, then saturated sodium
hydrogen carbonate solution (5 cm3) was added and the mixture
extracted with dichloromethane (3 × 10 cm3). The combined
organic layers were dried over MgSO4, filtered and concen-
trated in vacuo. The residue was redissolved in dichloromethane
(2 cm3) and piperidine (250 µl, 2.52 mmol) added at room tem-
perature. After stirring for 1 h, the solution was concentrated
in vacuo. Column chromatography (ethyl acetate–light petrol-
eum; 1 : 4) provided 9d (50 mg, 80%) as a colourless oil; [α]2D4
ϩ117 (c 1.0, CHCl3); νmax (neat)/cmϪ1 3340 (NH), 2930, 2857,
(100 MHz; CDCl ) 170.9 (C᎐O), 170.6 (C᎐O), 136.5 (C-2),
᎐
᎐
3
122.7 (C-3), 65.4 (C-4), 63.6 (C-6), 53.3 (C-1), 49.9 (C-5), 26.6
(CH2CH3), 21.1 (CH3), 20.9 (CH3), 10.9 (CH2CH3); m/z(ESϩ)
264 (M ϩ Naϩ), 242 (M ϩ Hϩ). HRMS (ESϩ); calcd for
C12H20NO4 (M ϩ Hϩ) 242.1392, found 242.1394. Further
elution gave 11 (29 mg, 40%) as a colourless oil; [α]2D3 ϩ161.0
(c 1.0, CHCl3); νmax (neat)/cmϪ1 3456 (NH), 3330 (NH), 3033,
2964, 2936, 2878, 1740 (C᎐O), 1240; δH (400 MHz; CDCl3) 5.99
᎐
(1H, dd, J2,3 10.0, 1.2, H-2), 5.94 (1H, ddd, J3,2 10.0, 4.8, 2.0,
H-3), 5.11–5.07 (1H, m, H-4), 4.17 (1H, dd, J6,6Ј 11.1, J6,5 6.3,
H-6), 4.06 (1H, dd, J6Ј,6 11.1, J6Ј,5 7.5, H-6Ј), 3.30–3.24 (1H, m,
H-1), 3.21–3.15 (1H, m, H-5), 2.07 (3H, s, CH3), 2.06 (3H, s,
CH3), 1.61 (1H, br s, NH), 1.55 (2H, quintet, J 7.4, CH2CH3),
2836, 1740 (C᎐O), 1238; δ (400 MHz; CDCl ) 5.82–5.77 (1H,
᎐
H
3
0.97 (3H, t, J 7.4, CH CH ); δ (100 MHz; CDCl ) 170.8 (C᎐O),
᎐
2
3
C
3
m, H-2), 5.63–5.58 (1H, m, H-3), 5.48 (1H, br s, ᎐CH ), 5.18–
᎐
170.7 (C᎐O), 137.5 (C-2), 123.1 (C-3), 65.2 (C-4), 64.3 (C-6),
᎐
5.13 (1H, m, H-4), 4.21 (1H, dd, J6,6Ј 11.3, J6,5 2.9, H-6), 4.01
(1H, dd, J6Ј,6 11.3, J6Ј,5 6.7, H-6Ј), 3.51–3.45 (1H, m, H-1), 3.01
(1H, ddd, J5,4 9.3, J5,6Ј 6.7, J5,6 2.9, H-5), 2.04 (3H, s, CH3), 2.03
(3H, s, CH3), 2.05–1.75 (6H, m, 3 × CH2), 1.81 (1H, br s, NH),
56.2 (C-1), 54.9 (C-5), 28.4 (CH2CH3), 21.1 (CH3), 20.9 (CH3),
10.0 (CH2CH3); m/z(ESϩ) 264 (M ϩ Naϩ), 242 (M ϩ Hϩ).
HRMS (ESϩ); calcd for C12H20NO4 (M ϩ Hϩ) 242.1392, found
242.1395.
1.62–1.51 (4H, m, 2 × CH ); δ (100 MHz; CDCl ) 170.8 (C᎐O),
᎐
2
C
3
170.6 (C᎐O), 134.5 (C-2), 133.6 (C), 125.1 (C-3), 124.8 (᎐CH),
᎐
᎐
68.1 (C-4), 64.9 (C-6), 55.9 (C-5), 51.9 (C-1), 44.5 (NCHCH2),
28.5 (CH2), 25.3 (CH2), 22.9 (CH2), 22.4 (CH2), 21.1 (CH3),
20.8 (CH3); m/z(ESϩ) 637 (2M ϩ Naϩ), 330 (M ϩ Naϩ), 308 (M
ϩ Hϩ), 264. HRMS (ESϩ); calcd for C17H26NO4 (M ϩ Hϩ)
308.1862, found 308.1854. Further elution gave 10d (6.0 mg,
10%) as a colourless oil; νmax (neat)/cmϪ1 3329 (NH), 2928,
12-ꢀ-(1,5-Anhydro-2,3-dideoxy-4,6-di-O-acetyl-1,5-imino-ꢀ-D-
erythro-hex-2-eno-pyranosyl)dodec-2-ene 14 and 12-ꢁ-(1,5-
anhydro-2,3-dideoxy-4,6-di-O-acetyl-1,5-imino-ꢁ-D-erythro-
hex-2-eno-pyranosyl)dodec-2-ene 28
To a stirred solution of trimethyl-(1-nonyl-allyl)-silane17c (110
mg, 0.457 mmol) in dichloromethane (3 ml) at Ϫ60 ЊC was
added 2 (150 mg, 0.304 mmol) dropwise followed by boron
trifluoride diethyl etherate (37.0 µl, 0.292 mmol). The resulting
mixture was stirred at Ϫ50 ЊC for 1.5 h then allowed to warm to
0 ЊC over 1.5 h. Saturated sodium hydrogen carbonate solution
(5 ml) was added, and the resulting mixture extracted with di-
chloromethane (3 × 10 ml). The combined organic layers were
dried over MgSO4, filtered and concentrated in vacuo. The resi-
due was redissolved in dichloromethane (3 ml) and piperidine
(400 µl, 4.04 mmol) at room temperature and stirred for 1 h,
then concentrated in vacuo. Column chromatography (ethyl
acetate–light petroleum; 1 : 40 increasing to 1 : 9) provided 14
(90 mg, 78%) as a colourless oil; [α]2D6 ϩ110.0 (c 1.0, CHCl3);
νmax (neat)/cmϪ1 3462 (NH), 3338 (NH), 3037, 2924, 2854, 1740
2856, 2838, 1743 (C᎐O), 1235; δ (400 MHz; CDCl ) 5.90–5.85
᎐
H
3
(1H, m, H-2), 5.70 (1H, dt, J 10.2, 2.3, H-3), 5.51 (1H, br s,
᎐CH ), 5.09–5.05 (1H, m, H-4), 4.18 (1H, dd, J6,6Ј 11.1, J6,5 4.0,
᎐
H-6), 4.01 (1H, dd, J6Ј,6 11.1, J6Ј5 7.9, H-6Ј), 3.48–3.42 (1H, m,
H-1), 3.24–3.19 (1H, m, H-5), 2.18–1.95 (6H, m, 3 × CH2), 2.08
(3H, s, CH3), 2.07 (3H, s, CH3), 1.80–1.44 (5H, m, NH, 2 ×
CH2); δC (100 MHz; CDCl ) 170.8 (C᎐O), 170.7 (C᎐O),
᎐
᎐
3
134.7 (C-2), 134.6 (C), 124.9 (᎐CH), 123.9 (C-3), 67.5 (C-4),
᎐
64.2 (C-6), 51.2 (C-5), 48.9 (C-1), 42.5 (NCHCH2), 28.2 (CH2),
25.4 (CH2), 22.9 (CH2), 22.4 (CH2), 21.2 (CH3), 20.8 (CH3);
m/z(ESϩ) 637 (2M ϩ Naϩ), 330 (M ϩ Naϩ), 308 (M ϩ Hϩ).
HRMS (ESϩ); calcd for C17H26NO4 (M ϩ Hϩ) 308.1862, found
308.1859.
(C᎐O), 1457, 1233; δ (400 MHz; CDCl3) 5.80 (1H, br d,
J2,3 10.1, H-2), 5.65 (1H, br d, J3,2 10.1, H-3), 5.53 (1H, m,
᎐
H
ꢀ-(1,5-Anhydro-2,3-dideoxy-4,6-di-O-acetyl-1,5-imino-ꢀ-D-
threo-hex-2-eno-pyranosyl)ethane 12 and ꢁ-(1,5-anhydro-2,3-
dideoxy-4,6-di-O-acetyl-1,5-imino-ꢁ-D-threo-hex-2-eno-pyrano-
syl)ethane 11
CH CH᎐CH), 5.33 (1H, m, CH CH᎐CH ), 5.15 (1H, dd,
᎐
᎐
2
2
J4,5 9.0, J4,3 1.8, H-4), 4.20 (1H, dd, J6,6Ј 11.3, J6,5 2.6, H-6), 4.03
(1H, dd, J6Ј,6 11.3, J6Ј,5 6.1, H-6Ј), 3.41 (1H, br s, H-1), 3.01 (1H,
ddd, J5,4 8.9, J5,6Ј 6.1, J5,6 2.6, H-5), 2.14 (2H, t, J 6.6,
To a stirred solution of 8 (150 mg, 0.304 mmol) in dichloro-
methane (2 cm3) at Ϫ20 ЊC was added diethylzinc (1.0 M in
hexane, 456 µl, 0.456 mmol), followed by boron trifluoride
diethyl etherate (43 µl, 0.339 mmol). The resulting solution was
allowed to warm to room temperature over 1 h, then stirred
for a further 1 h. Saturated sodium hydrogen carbonate
solution (5 cm3) was added, and the mixture extracted with
CHCH CH᎐CH), 2.06 (3H, s, CH ), 2.05 (3H, s, CH ), 1.99
᎐
2
3
3
(2H, m, ᎐CHCH CH ), 1.89 (1H, br s, NH), 1.40–1.20 (14H, m,
᎐
2
2
7 × CH2), 0.86 (3H, t, J 7.2, CH3); δC (100 MHz; CDCl3) 170.8
(C᎐O), 170.6 (C᎐O), 134.9 (CH CH᎐CH), 134.1 (C-2), 125.6
᎐
᎐
᎐
2
(C-3), 124.9 (CH CH᎐CH), 67.8 (C-4), 64.8 (C-6), 55.6 (C-5),
᎐
2
53.7 (C-1), 38.9 (CH CH᎐), 32.7 (CH CH᎐), 31.9 (CH ), 29.6
᎐
᎐
2
2
2
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 2 7 2 3 – 2 7 3 3
2730