4726 J. Am. Chem. Soc., Vol. 123, No. 20, 2001
OlliVier and Renaud
mg, 0.03 mmol) portions every 90 min. Filtration (hexane, hexane/
AcOEt 70:30 then 60:40) and FC (hexane/AcOEt 70:30) gave 30 (139
mg, 37%) as a white solid. For analytical purpose, a sample was
recrystallized from EtOH at 4 °C. Colorless crystals. Mp 102-103 °C.
3.08-3.04 (2.35%); 4.25-4.22 (EtOCHOCH) f 5.28-5.27 (1.59%),
2.20-2.14 (6.58%); 3.55-3.48 (CH CHHOCH) f 5.28-5.27 (4.38%),
3
3.81-3.74 (9.60%); 3.08-3.04 (MeOOCCH) f 5.28-5.27 (2.52%),
3.71-3.66 (4.89%); 2.20-2.14 (2.40%); 2.20-2.14 (MeOOCH-
2
2
13
[R]
D
+172.1 (c 0.380, CHCl
3
). IR (neat) 2966, 2118, 1753, 1431,
CHCHN
3
) f 4.25-4.22 (5.64%), 3.08-3.04 (2.42%). C NMR (125
-
1 1
1
369, 1236, 1111, 1066, 1043, 918 cm . H NMR (500 MHz, CDCl
3
)
MHz) δ 172.1, 105.4, 77.4, 64.3, 60.0, 55.1, 52.3, 45.8, 29.1, 27.5,
18.8, 15.3.32 (mixture of diastereomers): IR (neat) 2941, 2870, 2100,
δ 5.60 (d, J ) 4.3 Hz, 1H), 5.39 (t, J ) 9.7 Hz, 1H), 5.05 (t, J ) 10.1
Hz, 1H), 4.95 (dd, J ) 10.1, 4.4 Hz, 1H), 4.27 (dd, J ) 12.5, 4.6 Hz,
-
1
1738, 1439, 1377, 1201, 1095, 1010 cm . MS (CI, CH
4
) m/z 270
+
1
H), 4.18-4.12 (m, 2H), 2.11 (s, 3H), 2.10 (s, 3H), 2.03 (s, 3H), 2.02
(MH , 4), 224 (100), 195 (12), 181 (13), 153 (17), 136 (8). Anal. Calcd
13
(
s, 3H). C NMR (125 MHz, CDCl
3
) δ 170.5, 169.9 (2C), 169.4, 86.1,
). MS (CI, CH
m/z 331 (MH - HN , 100), 314 (14), 271 (27), 169 (52), 139 (14).
19 3 9
Anal. Calcd for C14H N O (373.32): C, 45.04; H, 5.13; N, 11.26.
19 3 4
for C12H N O (269.30): C, 53.52; H, 7.11; N, 15.60. Found: C, 53.62;
H, 7.10; N, 15.69.
7
0.1, 69.6, 69.5, 67.8, 61.5, 20.7, 20.6, 20.5 (2CH
3
4
)
+
3
3-Iodo-2-[(3-methyl-2-butenyl)oxy]tetrahydro-2H-pyran (33). To
a solution of 3-methyl 2-buten-1-ol (1.0 mL, 10.0 mmol) and 3,4-
dihydropyran (1.1 mL, 12.0 mmol) in dry CH Cl (10 mL) was added
Found: C, 45.13; H, 5.06; N, 11.16.
2
2
Methyl 3-(2-Cyclohexen-1-yloxy)-3-(ethyloxy)-2-iodopropanoate
N-iodosuccinimide (2.25 g, 10.0 mmol) portionwise at -30 °C under
. After 3 h, the reaction mixture was diluted with CH Cl (20 mL),
washed with water (20 mL), 10% Na (20 mL), and brine, dried
over MgSO , and concentrated in vacuo.The residue was purified by
FC (hexane/Et O 90:10) to afford 33 (2.76 g, 93%). Colorless oil. IR
(neat) 2945, 2853, 1439, 1377, 1354, 1201, 1122, 1068, 1018, 941,
(
31). To a solution of 2-cyclohexen-1-ol (1.1 mL, 11.0 mmol) and
N
2
2
2
41
methyl (E)-3-ethoxy-2-propenoate (1.69 g, 13.0 mmol) in dry CH
Cl
2 2
2 2 3
S O
(
10 mL) was added N-iodosuccinimide (2.92 g, 13.0 mmol) portionwise
4
at 0 °C under N
2
. After 30 h at room temperature, the reaction mixture
Cl (20 mL), washed with water (20 mL), 10%
(20 mL), and brine, dried over MgSO , and concentrated in
vacuo. The residue was purified by FC (hexane/AcOEt 95:5 then 90:
2
was diluted with CH
Na
2
2
-
1 1
S O
2 2 3
4
3
868 cm . H NMR (360 MHz, CDCl ) δ 5.36 (t, J ) 6.8 Hz, 1H),
4.66 (d, J ) 5.4 Hz, 1H), 4.21 (dd, J ) 11.7, 6.8 Hz, 1H), 4.12-3.96
(m, 3H), 3.58 (ddd, J ) 11.8, 7.3, 3.2 Hz, 1H), 2.42-2.34 (m, 1H),
1
1
0) to afford 31 (2.94 g, 86%) as a 50:50 mixture of two isomers ( H
NMR). Orange oil. IR (neat) 3028, 2934, 1740, 1437, 1373, 1346, 1304,
2.06-1.97 (m, 1H), 1.81-1.71 (m, 1H), 1.76 (s, 3H), 1.69 (s, 3H),
1
1
13
1
253, 1203, 1103, 1039, 941, 727 cm- . H NMR (360 MHz, CDCl
3
)
1.63-1.52 (m, 1H). C NMR (90 MHz, CDCl
3
) δ 137.9, 120.0, 101.3,
+
δ 5.90-5.82 (m, 2H, two diastereomers), 5.71-5.62 (m, 2H, two
diastereomers), 5.07 (d, J ) 2.7 Hz, 1H, one diast.), 5.04 (d, J ) 2.7
Hz, 1H, one diastereomer), 4.44 (s, 1H, one diastereomer), 4.42 (s,
64.4, 63.4, 32.7, 29.5, 25.7, 25.5, 18.0. MS (CI, CH
4
) m/z 297 (MH ,
2
1), 211 (18), 70 (100). Anal. Calcd for C10H17IO (296.15): C, 40.56;
H, 5.79. Found: C, 40.63; H, 5.74.
1
(
2
H, one diastereomer), 4.20-4.13 (m, 2H, two diastereomers), 3.74
s, 6H, two diastereomers), 3.71-3.57 (m, 4H, two diastereomers),
.08-1.47 (m, 12H, two diastereomers), 1.25 (t, 6H, two diastereomers).
3
3-(1-Azido-1-methylethyl)hexahydro-4H-furo[2,3-b]pyran (34).
34 was prepared according to procedure D from 33 (296 mg, 1.0 mmol),
PhSO N (550 mg, 3.0 mmol), (Bu Sn) (0.76 mL, 1.5 mmol), and
2 3 3 2
1
C NMR (90 MHz, CDCl
diastereomer), 131.1 (one diastereomer), 127.1 (one diastereomer), 126.7
one diastereomer), 101.4 (one diastereomer), 100.5 (one diastereomer),
2.1 (one diastereomer), 71.1 (one diastereomer), 60.6 (one diastere-
3
) δ 169.6 (two diastereomers), 131.5 (one
DTBHN (11 mg, 0.06 mmol). Filtration (hexane then hexane/AcOEt
70:30) and FC (hexane/AcOEt 80:20) gave 34 (193 mg, 91%) as a
1
(
7
61:39 mixture of two isomers ( H NMR). Colorless oil. IR (neat) 2939,
-
1 1
2887, 2100, 1450, 1371, 1263, 1149, 1037, 953, 897 cm . H NMR
(500 MHz, CDCl ) δ 5.23 (d, J ) 3.5 Hz, 1H, one diastereomer), 5.02
omer), 60.1 (one diastereomer), 52.7 (one diastereomer), 52.6 (one
diastereomer), 29.6 (one diastereomer), 27.9 (one diastereomer), 24.9
3
(d, J ) 3.8 Hz, 1H, one diastereomer), 4.16 (t, J ) 8.9 Hz, 1H, one
diastereomer), 4.00 (dd, J ) 11.0, 7.9 Hz, 1H, one diastereomer), 3.92-
3.87 (m, 1H, one diastereomer), 3.90 (t, J ) 7.9 Hz, 1H, one
diastereomer), 3.80-3.75 (m, 2H, two diastereomers), 3.67-3.63 (m,
1H, one diastereomer), 3.44 (ddd, J ) 11.5, 10.7, 2.6 Hz, 1H, one
diastereomer), 2.33-2.28 (m, 2H, two diastereomers), 2.10-1.38 (m,
(
2
one diastereomer), 24.8 (one diastereomer), 21.3 (one diastereomer),
1.0 (one diastereomer), 18.9 (one diastereomer), 18.4 (one diastere-
omer), 15.0 (one diastereomer), 14.9 (one diastereomer). MS (CI, CH
4
)
m/z 257 (50), 225 (39), 207 (10), 131 (33), 103 (20), 97 (82), 82 (100),
+
69 (9). HRMS for C12
H20IO
4
[MH ]: calcd 355.0408; found 355.0402.
1
0H, two diastereomers), 1.39 (s, 3H, one diastereomer), 1.31 (s, 3H,
one diastereomer), 1.30 (s, 3H, one diastereomer), 1.27 (s, 3H, one
diastereomer). 13C NMR (90 MHz, CDCl
) δ 102.2, 101.2, 69.0, 64.6,
4.2, 62.7, 60.9, 60.3, 50.4, 47.9, 39.6, 36.3, 26.7, 25.5, 24.8, 24.5,
Methyl 4-Azido-2-(ethyloxy)octahydro-1-benzofuran-3-carbox-
ylate (32). 32 was prepared according to procedure D from 31 (354
mg, 1.0 mmol), PhSO (550 mg, 3.0 mmol), (Bu Sn) (0.76 mL, 1.5
mmol), and DTBHN (11 mg, 0.06 mmol). Filtration (hexane then
hexane/AcOEt 80:20) and three successive FCs (hexane/AcOEt 95:5,
N
2 3
3
2
3
6
2
1
+
3.9, 23.2, 20.8, 20.1. MS (CI, CH
4
) m/z 212 (MH , 21), 184 (44),
69 (62), 154 (28), 139 (100), 100 (50), 71 (17), 98 (29), 58 (18).
9
0:10 then 80:20) gave 32 (207 mg, 77%) as a 53:47 mixture of two
1
1
10 17 3 2
Anal. Calcd for C H N O (211.26): C, 56.85; H, 8.11; N, 19.89.
Found: C, 56.83; H, 8.20; N, 19.94.
3-Iodo-2-(2-propenyloxy)tetrahydro-2H-pyran (35). To a solution.
of allylic alcohol (0.68 mL, 10.0 mmol) and 3,4-dihydropyran (1.1 mL,
diastereomers ( H NMR). Colorless oil. 32a (less polar): H NMR (500
MHz, CDCl
3
) δ 5.48 (d, J ) 4.9 Hz, 1H), 4.32-4.29 (m, 1H), 3.76
qd, J ) 9.5, 7.1 Hz, 1H), 3.75 (s, 1H), 3.50 (qd, J ) 9.5, 7.1 Hz, 1H),
(
3
.31 (ddd, J ) 12.1, 10.6, 4.3 Hz, 1H), 3.12 (dd, J ) 6.6, 4.9 Hz, 1H),
.20 (ddd, J ) 10.5, 6.6, 3.5 Hz, 1H), 2.08-2.00 (m, 2H), 1.68-1.45
2
12 mmol) in dry CH
g, 10.0 mmol) portionwise at -30 °C under N
mixture was diluted with CH Cl (20 mL), washed with water (20 mL),
10% Na (20 mL), and brine, dried over MgSO , and concentrated
in vacuo. The residue was purified by FC (hexane/Et O 90:10) to afford
35 (2.56 g, 95%). Colorless oil. IR (neat) 2945, 2851, 1435, 1377,
2
Cl
2
(10 mL) was added N-iodosuccinimide (2.25
(
m, 3H), 1.36-1.27 (m, 3H), 1.19 (t, J ) 7.1 Hz, 3H). NOE difference
2
. After 3 h, the reaction
spectra for 32a (less polar) (500 MHz): 5.49-5.47 (EtOCH) f 3.74-
.76 (5.27%), 3.36-3.29 (3.55%); 4.32-4.29 (EtOCHOCH) f 3.14-
.11 (4.08%), 2.22-2.17 (6.53%); 3.36-3.29 (N CH) f 5.49-5.47
3.52%); 3.14-3.11 (MeOOCCH) f 5.49-5.47 (1.56%), 4.32-4.29
3.24%); 2.22-2.17 (6.17%); 2.22-2.17 (MeOOCHCHCHN ) f
.32-4.29 (5.78%); 3.14-3.11 (7.60%). 13C NMR (125 MHz) δ 171.5,
04.8, 77.1, 64.3, 58.0, 55.2, 52.1, 47.6, 30.2, 26.8, 18.8, 15.2.
2b (more polar): 1H NMR (500 MHz, CDCl
) δ 5.28 (d, J ) 1.9
Hz, 1H), 4.25-4.22 (m, 1H), 3.78 (qd, J ) 9.5, 7.1 Hz, 1H), 3.74 (s,
2
2
3
3
(
S O
2 2 3
4
3
2
-
1
1
(
4
1
3
1352, 1201, 1122, 1068, 1026, 943, 866, 696 cm . H NMR (360
MHz, CDCl ) δ 5.99-5.88 (m, 1H), 5.33 (d, J ) 17.2 Hz, 1H), 5.21
3
(d, J ) 10.4 Hz, 1H), 4.68 (d, J ) 5.4 Hz, 1H), 4.26 (dd, J ) 12.7, 5.4
Hz, 1H), 4.14-3.96 (m, 3H), 3.59 (ddd, J ) 11.3, 7.7, 3.6 Hz, 1H),
3
3
2
1
6
1
.43-2.34 (m, 1H), 2.07-1.97 (m, 1H), 1.82-1.73 (m, 1H), 1.63-
.53 (m, 1H). 13C NMR (90 MHz, CDCl
3.3, 32.6, 29.2, 25.5. MS (CI, CH
) δ 133.9, 117.3, 101.4, 68.8,
3
1
1
2
H), 3.68 (ddd, J ) 10.9, 9.5, 4.3 Hz, 1H), 3.52 (qd, J ) 9.5, 7.1 Hz,
H), 3.06 (t, J ) 2.2 Hz, 1H), 2.18 (ddd, J ) 9.3, 4.8, 2.5 Hz, 1H),
.06-1.95 (m, 2H), 1.67-1.53 (m, 3H), 1.43-1.36 (m, 3H), 1.22 (t, J
+
4
) m/z 269 (MH , 1), 211 (100),
8 2
41 (90), 101 (22), 85 (21), 72 (14), 56 (6). Anal. Calcd for C H13IO
(
268.09): C, 35.84; H, 4.89. Found: C, 35.95; H, 4.84.
-(Azidomethyl)hexahydro-4H-furo[2,3-b]pyran (36). 36 was
prepared according to procedure D from 35 (268 mg, 1.0 mmol),
PhSO (550 mg, 3.0 mmol), (Bu Sn) (0.76 mL, 1.5 mmol), and
DTBHN (70 mg, 0.40 mmol) added by (5.2 mg, 0.03 mmol) portions
)
7.1 Hz, 3H). NOE difference spectra for 32b (more polar) (500
3
MHz): 5.28-5.27 (EtOCH) f 4.25-4.22 (1.34%), 3.55-3.48 (4.70%),
(
41) Tietze, L.-F.; Meier, H.; Voss, E. Synthesis 1988, 274. Weiguny,
J.; Sch a¨ fer, H. J. Liebigs Ann. Chem. 1994, 225.
N
2 3
3
2