Sape S. Kinderman et al.
FULL PAPERS
d 138.2, 137.5, 128.0, 127.0, 125.8, 124.3, 114.1, 114.0, 97.8,
Methyl 6-Benzyloxy-2-methyl-3,6-dihydro-2H-pyran-
2-carboxylate (35)
96.1, 73.3, 72.4, 70.9, 65.7, 55.1, 25.9, 25.8; HRMS (FAB): calcd.
for C16H21O3 (MH ): 261.1491; found: 261.1491.
Precursor 12 (137 mg, 0.47 mmol) was reacted following the
general method. Column chromatography (heptane/ethyl
acetate, 9:1 3:1) afforded 35 as two separated diastereoisom-
ers; yield: 95 mg (0.36 mmol, 77%). Diastereoisomer 1:
1HNMR (300 MHz, CDCl 3): d 7.37 7.22 (m, 5H), 6.08
5.68 (m, 1H), 5.74 5.68 (m, 1H), 5.09 5.07 (m, 1H), 4.75
(AB, J 12.2, 76.0 Hz, 2H), 3.55 (s, 3H), 2.76 (m, 1H), 2.08 (dq,
J 2.2, 2.5, 17.6 Hz, 1H), 1.50 (s, 3H); 13C NMR (50 MHz,
CDCl3): d 183.9, 138.7, 128.9, 128.3, 128.3, 128.1, 124.7, 94.3,
73.0, 69.8, 52.8, 32.4, 27.5. Diastereoisomer 2: 1HNMR
(300 MHz, CDCl3): d 7.39 7.24 (m, 5H), 6.00 5.94 (m,
1H), 5.76 5.70 (m, 1H), 5.43 5.41 (m, 1H), 4.76 (AB, J 11.8,
73.8 Hz, 2H), 3.75 (s, 3H), 2.60 (m, 1H), 2.26 (m, 1H), 1.58 (s,
3H); 13C NMR (50 MHz, CDCl3): d 175.0, 138.6, 128.9, 128.5,
128.1, 127.3, 126.2, 94.9, 76.2, 69.8, 53.0, 33.1, 25.7.
2-Methoxy-1-(4-toluenesulfonyl)-2,5-dihydro-1H-
pyrrole (39)
Precursor 25 (0.5 g, 1.78 mmol) was reacted according to the
general procedure. Column chromatography (petroleum
ether/diethyl ether, 9:1) gave 39 as a brown oil; yield: 0.43 g
À
1
1
(1.69 mmol, 95%); IR (film): n 2934, 1339 cm ; HNMR
(C6D6, 400 MHz): d 7.76 (d, J 8.3 Hz, 2H), 6.78 (d, J
8.0 Hz, 2H), 5.97 (d, J 3.4 Hz, 1H), 5.22 5.15 (m, 2H), 3.88
(dd, J 15.5, 2.1 Hz, 1H), 3.68 (m, 1H), 3.12 (s, 3H), 1.88 (s,
3H); 13C NMR (C6D6, 100 MHz): d 143.7, 130.0, 128.3, 128.0,
127.9, 127.6, 127.5, 96.7, 55.1, 53.1; HRMS (FAB): calcd. for
C12H16NO3S (MH ): 254.0851; found: 254.0851.
2-Benzyloxy-2H-chromene (36)
6-Benzyloxy-1-(4-toluenesulfonyl)-1,2,3,6-
tetrahydropyridine (40)
Precursor 13 (0.20 g, 0.76 mmol) was reacted according to the
general procedure. Column chromatography (petroleum
ether/ethyl acetate, 40:1) afforded 36 as a slightly brown oil;
Precursor 26 (0.2 g, 0.54 mmol) was reacted according to the
general procedure. Column chromatography (pentane/diethyl
ether, 4:1 2:1) afforded 40 as a colorless oil; yield: 0.13 g
yield: 0.14 g (0.59 mmol, 78%); IR (film): n 3032, 2919, 1202,
À
1
1
1031 cm ; HNMR (C 6D6, 400 MHz): d 7.20 (m, 2H), 7.05
(m, 3H), 6.97 (m, 2H), 6.85 (br. d, J 7.2 Hz, 1H), 6.77 (m, 1H),
6.36 (d, J 9.2 Hz, 1H), 5.55 (m, 2H), 4.74 (d, J 12.1 Hz, 1H),
4.50 (d, J 12.1 Hz, 1H); 13C NMR (C6D6, 50 MHz): d 151.7,
137.9, 129.0, 127.8, 127.5 (2Â), 127.1 (2Â), 126.7, 126.1, 121.1,
120.8, 119.8, 116.4, 94.2, 68.8; HRMS (FAB): calcd. for
(0.37 mmol, 68%); IR (film): n 3533, 3022, 2828, 1595, 1450,
À
1322, 1156 cm ; 1HNMR (CDCl 3, 500 MHz): d 7.72 (d, J
1
8.3 Hz, 2H), 7.39 7.32 (m, 5H), 7.27 (d, J 8.0 Hz, 2H), 5.85
5.78 (m, 2H), 5.52 (d, J 3.7 Hz, 1H), 4.80 (d, J 11.7 Hz, 1H),
4.64 (d, J 12.0 Hz, 1H), 3.83 3.80 (m, 1H), 3.45 3.39 (m,
1H), 2.43 (s, 3H), 1.78 1.76 (m, 2H); 13C NMR (CDCl3,
125 MHz): d 143.3, 138.3, 137.9, 129.5, 129.2, 128.3, 128.0,
127.6, 126.9, 124.7, 79.5, 69.6, 37.6, 23.0, 21.4; HRMS (FAB):
C16H15O2 (MH ): 239.1072; found: 239.1060.
calcd. for C19H22NO3S (MH ): 344.1320; found: 344.1316.
2-Benzyloxy-4-methyl-2H-chromene (37)
Precursor 14 (0.44 g, 1.58 mmol) was reacted according to the
general method. Column chromatography (petroleum ether/
ethyl acetate, 20:1) afforded 37 as a brown oil; yield: 0.33 g
2-Benzyloxy-5-benzyloxymethyl-1-(4-
nitrobenzenesulfonyl)-2,5-dihydro-1H-pyrrole (41)
À
1
(1.31 mmol, 84%); IR (film): n 3031, 2915, 1215, 1037 cm ;
1HNMR (C 6D6, 400 MHz) d 7.23 7.20 (m, 2H), 7.12 7.04
(m, 6H), 6.85 6.81 (m, 1H), 5.58 (d, J 3.8 Hz, 1H), 5.42 (m,
1H), 4.78 (d, J 12.1 Hz, 1H), 4.53 (d, J 12.1 Hz, 1H), 1.76 (s,
3H); 13C NMR (C6D6, 50 MHz): d 151.3, 138.6, 132.1, 128.9,
127.9 (2Â), 127.5 (2Â), 127.1, 123.6, 121.0, 118.6, 117.3, 116.5,
Precursor 27 (0.1 g, 0.2 mmol) was reacted following the
general method, except that catalyst 31 was used in toluene at
60 8C. Column chromatography (pentane/diethyl ether, 2:1)
yielded 41 as a colorless oil; yield: 40.0 mg (0.084 mmol, 42%);
À
1
IR (film): n 2920, 1715, 1529 cm ; 1HNMR (CDCl 3,
400 MHz): both diastereoisomers: d 8.15 (m, 2H), 7.97 (m,
2H), 7.45 7.07 (m, 10H), 6.11 (m, 1H), 5.76 (m, 1H), 4.61 4.30
(m, 6H), 3.68 (m, 2H); 13C NMR (CDCl3, 100 MHz): both
diastereoisomers: d 137.4, 132.5, 128.6, 128.3, 128.3, 127.8,
127.7, 127.6, 127.5, 127.3, 123.9, 94.4, 73.4, 72.4, 68.0, 65.7, 65.3,
94.4, 68.8, 17.3; HRMS (FAB): calcd. for C17H16O2 (MH ):
252.1150; found: 252.1158.
2-Benzyloxymethyl-6-methoxy-4-vinyl-3,6-dihydro-
2H-pyran (38)
29.6; HRMS (FAB): calcd. for C25H24N2O6SNa (MNa ):
503.1253; found: 503.1250.
Precursor 18 (0.24 g, 0.92 mmol) was reacted as indicated in the
general procedure. Column chromatography (petroleum
ether/diethyl ether, 20:1) afforded the dihydropyran 38 as a
colorless oil; yield: 85.0 mg (0.33 mmol, 36%); IR (film): n
Methyl 6-Benzyloxy-1-(4-nitrobenzenesulfonyl)-
1,2,3,6-tetrahydropyridine-2-carboxylate (42)
À
1
3088, 3030, 2825, 1652 cm ; 1HNMR (CDCl 3, 400 MHz): both
diastereoisomers: d 7.39 7.26 (m, 5H), 6.37 (dd, J 17.5,
10.7 Hz, 1H), 5.70 and 5.63 (s, 1H), 5.29 and 5.24 (d, J 6.8 Hz,
1H), 5.14 (s, 1H), 5.11 and 5.03 (s, 1H), 4.62 (m, 2H), 4.18 4.04
(m, 1H), 3.72 3.58 (m, 2H), 3.49 and 3.46 (s, 3H), 2.22 2.16
(m, 2H); 13C NMR (100 MHz, CDCl3): both diastereoisomers:
Precursor 28 (3.1 g, 6.7 mmol) was reacted according to the
general method. Column chromatography (pentane/diethyl
ether, 1:1 1:4) afforded 42 as a white solid; yield: 2.59 g
(6.0 mmol, 89%); mp 106 108 8C; IR (film): n 3105, 2952,
À
1
1743, 1529, 1349, 1167 cm ; 1HNMR (CDCl 3, 400 MHz): both
744
Adv. Synth. Catal. 2002, 344, 736 748