Hydride-Transfer Domino Rearrangement
J . Org. Chem., Vol. 67, No. 5, 2002 1635
Sch em e 14
(2H, s, OCHN), 4.71 (1H, s, OCHO); 13C NMR (acetonitrile-
d3:D2O ) 12:5, 125.7 MHz) δ 28.35 (CH3), 28.79 (CH3), 35.86
[(CH2)2CCH3], 35.91 [(CH2)2CCH3], 42.79 (CCH2C), 43.79
(CCH2C), 54.53 (CH2N), 89.17 (OCHN), 100.11 (OCHO), 178.17
mixed with an aqueous solution (5 mL) of glycine (17.7 mg,
0.24 mmol) and NaHCO3 (20.7 mg, 0.25 mmol). After the
mixture had been reacted at room temperature for 5 days with
stirring, volatiles were removed under reduced pressure.
Lactone-imine 9-Na was obtained by washing with acetonitrile
(68.6 mg, 0.24 mmol, 96%). Further purification was carried
out by HPLC (TSK-GEL Amide-80), using CH3CN/H2O (3:1)
as an eluent. 9-Na : colorless solids; 1H NMR (acetonitrile-d3:
D2O ) 12:5, 500 MHz) δ 0.97 (3H, s, CH3), 0.98 (3H, s, CH3),
(COO); MS (ESI) m/z 555 [28, 2M- - Na], 284 [100, M-
-
Na + H2O], 266 [48, M- - Na].
The similar manner that was employed in the preparation
of dioxa-azawurtzitane 7-Na was used with trialdehyde 2 (30.9
mg, 0.15 mmol), Gly-His-Lys‚AcOH‚H2O (32.5 mg, 0.078
mmol), and NaHCO3 (13.0 mg, 0.16 mmol). Dioxa-azawurtzi-
tanes 8-Na was afforded in 86% yield (49.6 mg, 0.066 mmol).
8-Na : colorless solids; 1H NMR (acetone-d6:D2O ) 8:5, 500
MHz) δ 0.86 (CH3), 0.87 (CH3), 0.88 (CH3), 3.99 (OCHN), 4.01
(OCHN), 4.03 (OCHN), 4.65 (OCHO), 4.68 (OCHO); MS (ESI)
m/z 723 [100, M- - Na].
2
2
1.05 (1H, d, J HH ) 14.1 Hz, CHaHe), 1.23 (1H, d, J HH ) 13.7
2
Hz, CHaHe), 1.26 (3H, s, CH3), 1.30 (1H, d, J HH ) 12.8 Hz,
2
CHaHe), 1.55 (1H, d, J HH ) 12.8 Hz, CHaHe), 2.34 (1H, d,
2
2J HH ) 14.1 Hz, CHaHe), 2.51 (1H, d, J HH ) 13.7 Hz, CHaHe),
2
2
3.47 (1H, d, J HH ) 15.9 Hz, CH2O), 3.57 (1H, d, J HH ) 15.9
2
Hz, CH2O), 4.02 (1H, d, J HH ) 16.2 Hz, NCH2CO), 4.35 (1H,
d, J HH ) 16.2 Hz, NCH2CO), 8.15 (1H, s, CH)NCH2); 13C
2
Meth yl (1,7,9-Tr im eth yl-3,5-d ioxa -12-a za w u r tzita n o)-
a ceta te (7-Me). An acetonitrile solution (4 mL) of trialdehyde
2 (46.1 mg, 0.22 mmol) was mixed with an aqueous solution
(2.5 mL) of glycine methyl ester hydrochloride (26.5 mg, 0.21
mmol) and NaHCO3 (17.9 mg, 0.21 mmol). After the mixture
had been reacted at room temperature for 1.5 h with stirring,
volatiles were removed under reduced pressure. After being
extracted with CH2Cl2, the solvent was removed under reduced
pressure. Dioxa-azawurtzitane 7-Me was purified by molecular
distillation (56.9 mg, 0.20 mmol, 96%). 7-Me: colorless solids;
NMR (acetonitrile-d3:D2O ) 12:5, 125.7 MHz) δ 24.78 (CH3),
28.09 (CH3), 30.21 (CH3), 32.03 [(CH2)2CCH3], 39.38 [(CH2)2-
CCH3], 40.68 (CCH2C), 43.93 [(CH2)2CCH3], 47.69 (CCH2C),
47.83 (CCH2C), 62.62 (CH2O), 63.87 (NCH2CO), 170.01 (COO),
183.83 (COO), 187.32 (CHdNCH2); MS (ESI) m/z 555 [35,
2M- - Na], 266 [100, M- - Na]. Anal. Calcd for C14H20NNaO4‚
1.5H2O: C, 53.16; H, 7.33; N, 4.43. Found: C, 53.32; H, 7.72;
N, 4.74.
The similar manner using excesses of glycine and NaHCO3
2
1H NMR (acetonitrile-d3, 500 MHz) δ 0.80 (1H, d, J HH ) 11.6
10
10
gave tricycle 13-Na 2 as a byproduct. Tricycle 13-Na 2 was
recrystallized from CH3OH/CH3CN. 13-Na 2: colorless solids;
1H NMR (acetonitrile-d3:D2O ) 12:5, 500 MHz) δ 0.76 (1H, d,
2J HH ) 11.9 Hz, CHaHe), 0.89 (3H, s, CH3), 0.98 (3H, s, CH3),
2
Hz, CHaHe), 0.88 (2H, d, J HH ) 12.2 Hz, CHaHe), 0.98 (3H, s,
2
CH3), 1.00 (6H, s, CH3), 1.32 (2H, d, J HH ) 12.2 Hz, CHaHe),
2
1.47 (1H, d, J HH ) 11.6 Hz, CHaHe), 3.65 (3H, s, CH3OCO),
2
3.84 (2H, s, NCH2CO), 4.12 (2H, s, OCHN), 4.70 (1H, s,
OCHO); 13C NMR (acetonitrile-d3, 125.7 MHz) δ 28.40 (CH3),
28.95 (CH3), 35.88 [(CH2)2CCH3], 36.05 [(CH2)2CCH3], 42.76
(CCH2C), 44.25 (CCH2C), 51.77 (CH2N), 52.09 (CH3O), 88.90
1.03 (1H, d, J HH ) 12.3 Hz, CHaHe), 1.09 (3H, s, CH3), 1.11
2
2
(1H, d, J HH ) 13.7 Hz, CHaHe), 1.47 (1H, d, J HH ) 13.7 Hz,
2
CHaHe), 1.71 (1H, d, J HH ) 11.9 Hz, CHaHe), 1.81 (1H, d,
2J HH ) 12.2 Hz, CHaHe), 1.94 (1H, d, J HH ) 12.1 Hz, CH2N),
2
2
2
(OCHN), 99.99 (OCHO), 172.24 (COO). Anal. Calcd for C15H23
-
2.37 (1H, d, J HH ) 12.1 Hz, CH2N), 2.96 (1H, d, J HH ) 15.7
2
NO4: C, 64.04; H, 8.24; N, 4.98. Found: C, 64.42; H, 8.24; N,
4.91.
Sod iu m [(1,5,7-Tr im et h yl-2-oxo-3-oxa -b icyclo[3.3.1]-
n on -7-ylm eth ylen e)a m in o]a ceta te (9-Na ). An acetonitrile
solution (8 mL) of trialdehyde 2 (51.8 mg, 0.25 mmol) was
Hz, NCH2CO), 3.11 (1H, d, J HH ) 15.7 Hz, NCH2CO), 3.28
2
2
(1H, d, J HH ) 16.5 Hz, NCH2CO), 4.16 (1H, d, J HH ) 16.5
Hz, NCH2CO), 4.23 (1H, s, NCHN);13C NMR (acetonitrile-d3:
D2O ) 12:5, 125.7 MHz) δ 26.84 (CH3), 29.45 (CH3), 31.83
(CH3), 32.33 [(CH2)2CCH3], 35.45 [(CH2)2CCH3], 40.45 [(CH2)2-