Recyclable Pseudoephedrine Resins
as a colorless oil: m/z (CI+ mode, isobutane) 143 ((M + H)+,
) 3.8, 4.9 Hz, CH thiophene), 3.22-3.15 (1H, m, CHBu), 1.84-
1.69 (1H, m, 1H of CH2), 1.69-1.53 (4H, m, CH2, CH, 1H of
CH2), 1.52-1.44 (2H, m, CH2), 1.43-1.36 (4H, m, CH2, 1H of
CH2, 1H of CH2), 1.22-1.16 (4H, m, 2 × CH2), 1.03-1.00 (2H,
m, CH2), 0.78 (3H, t, J ) 7.0 Hz, CH3); 13C NMR (100 MHz,
CDCl3) δ 198.2 (CdO), 146.0 (C thiophene), 134.0 (CH
thiophene), 131.8 (CH thiophene), 128.5 (CH thiophene), 48.1
(CHBu), 39.8 (CH2), 38.6 (CH), 33.6 (CH2), 33.5 (CH2), 33.1
(CH2), 30.3 (CH2), 25.5 (2 × CH2), 23.2 (CH2), 14.3 (CH3).
100), 125 (22) and 83 (14); HRMS calcd for (M + H)+, C9H19
O
143.1436, found 143.1433; νmax (neat/cm-1) 3336s (OH), 2927s,
2860s, 2360s, 2339s; [R]D +1.15 (c ) 0.78 in CHCl3); 1H NMR
(400 MHz, CDCl3) δ 5.75-5.65 (1H, m, CH ) CH2), 4.97-4.88
(2H, m, CH2dCH), 3.47-3.39 (2H, m, CH2OH), 2.02-1.98 (2H,
m, CH2CHdCH2), 1.50-1.44 (2H, br m, OH and CH) 1.25-
1.15 (6H, m, 3 × CH2), 0.78 (3H, t, J ) 6.7 Hz, CH3); 13C NMR
(100 MHz, CDCl3) δ 137.5 (CHdCH2), 116.5 (CH2dCH), 65.9
(CH2OH), 40.8 (CH), 36.2 (CH2CHdCH2), 30.7 (CH2), 29.5
(CH2), 23.4 (CH2), 14.4 (CH3).
Further elution then gave 12 (16.1 mg,17%) as a yellow oil:
m/z (EI+ mode) 348 (M+, 2), 195 (100) and 111(40); HRMS calcd
for M+, C20H28OS2 348.1582, found 348.1582; νmax (neat)/cm-1
3537m (OH), 2951s, 2860s; 1H NMR (400 MHz, CDCl3) δ 7.14-
7.12 (2H, m, 2 × CH thiophene), 6.94-6.86 (4H, m, 4 × CH
thiophene), 2.14-2.10 (1H, m, CHBu), 1.65-1.64 (3H, m, CH,
CH2), 1.55-1.37 (8H, m, 3 × CH2, 2 × 1H of CH2), 1.28-1.19
(1H, m, 1H of CH2), 1.17-1.06 (3H, m, CH2, 1H of CH2), 0.94-
0.93 (2H, m, CH2), 0.73 (3H, t, J ) 7.0 Hz, CH3); 13C NMR
(100 MHz, CDCl3) δ 152.1 (C thiophene), 151.9 (C thiophene),
127.0 (CH thiophene), 124.6 (CH thiophene), 124.2 (CH
thiophene), 50.3 (COH), 50.3 (CHBu), 39.0 (CH), 37.9 (CH2),
34.0 (CH2), 32.6 (CH2), 31.9 (CH2), 31.7 (CH2), 25.4 (CH2), 25.3
(CH2), 14.4 (CH3).
(2S)-2-Ben zylp en ta n -1-ol 10f.24 Cleavage, after purifica-
tion by flash chromatography on silica (eluting with 20%
EtOAc/petroleum ether (40-60 °C)), gave alcohol 10f (60 mg,
59%) as a colorless oil: m/z (EI+ mode) 178 (M+, 31), 160 (24),
131 (21), 117 (50), 104 (49), 91 (100), 82 (52), 69 (16), 65 (12)
and 41 (11); HRMS calcd for M+, C12H18O 178.1358, found
178.1357; νmax (neat)/cm-1 3350s (OH), 2956s, 2927s, 1583w,
1
1542m, 1454s; [R]D +0.29 (c ) 1.39 in CHCl3); H NMR (400
MHz, CDCl3) δ 7.21-7.09 (5H, m, ArH), 3.43 (2H, apparent
d, J ) 5.3 Hz, CH2OH), 2.60-2.51 (2H, m, CH2Ph), 1.77-1.68
(1H, m, CH), 1.37-1.14 (4H, m, CH2CH3 and CH2CH2CH3),
0.83-0.80 (3H, t, J ) 7.0 Hz, CH3); 13C NMR (100 MHz, CDCl3)
δ 139.8 (ArC), 127.9 (2 × ArCH), 127.3 (2 × ArCH), 124.8
(ArCH), 63.8 (CH2OH), 41.3 (CHCH2Ph), 36.6 (CH2Ph), 32.0
(CH2CH2CH3), 19.1 (CH2CH3), 13.3 (CH3).
(2S)-2-Ben zyl-1-(th ien -2-yl)p en t-4-en -1-on e 11o. Cleav-
age, after purification using flash chromatography on silica
(eluting with 5% EtOAc/petroleum ether (40-60 °C)), gave 11o
(52.5 mg, 61%) as a yellow oil: m/z (EI+ mode) 256 (M+, 12),
215 (100), 212 (11), 131 (13), 111 (71) and 83 (56); HRMS calcd
(2S)-2-P r op ylh exa n -1-ol 10g.25 Cleavage, after purifica-
tion by flash chromatography on silica (eluting with 10%
EtOAc/petroleum ether (40-60 °C)), gave 10g (38.5 mg, 39%)
as a colorless oil: m/z (CI+ mode, ammonia) 162 ((M + NH4)+,
28), 131 (28), 130 (7) and 102 (8); νmax (neat/cm-1) 3336s (OH),
2956s, 2871s, 2360s, 2341s; [R]D +21.1 (c ) 0.09 in CHCl3);
1H NMR (400 MHz, CDCl3) δ 3.41 (2H, apparent d, J ) 5.5
Hz, CH2OH), 1.38-1.26 (2H, m, CH2OH and CH), 1.26-1.08
(10H, m, 5 × CH2), 0.78 (6H, 2 × t, J ) 7.0, 6.9 Hz, 2 × CH3-
CH2); 13C NMR (100 MHz, CDCl3) δ 66.1 (CH2OH), 40.7 (CH),
33.6 (2 × CH2), 31.0 (CH2), 29.5 (CH2), 23.5 (CH2), 14.8 (CH3-
CH2), 14.4 (CH3CH2).
for M+, C16H16OS 256.0922, found 256.0923; νmax (neat/cm-1
)
3077m (CdC), 2921m, 1654s (CdO), 1415s, 993m (CdCH2),
1
916s (CdCH2); [R]D +82.1 (c ) 1.33 in CHCl3); H NMR (400
MHz, CDCl3) δ 7.50-7.49 (2H, m, 2 × CH thiophene), 7.09-
7.04 (5H, m, ArH), 6.98-6.95 (1H, m, CH thiophene), 5.72-
5.61 (1H, m, CH ) CH2), 5.00-4.90 (2H, m, CH2dCH), 3.52-
3.43 (1H, m, CH), 3.01 (1H, dd, J ) 7.9, 13.6, 1H of CH2Ph),
2.74 (1H, dd, J ) 6.4, 13.6 Hz, 1H of CH2Ph), 2.51-2.44 (1H,
m, 1H of CH2CHdCH2), 2.27-2.21 (1H, m, 1H of CH2CHd
CH2); 13C NMR (100 MHz, CDCl3) δ 196.0 (CdO), 145.1 (ArC
or C thiophene), 139.8 (ArC or C thiophene), 135.6 (CHdCH2),
134.4 (CH thiophene), 132.2 (CH thiophene), 129.7 (2 × ArCH),
128.8 (2 × ArCH), 128.5 (ArCH), 126.7 (CH thiophene), 117.7
(CH2dCH), 50.6 (CH), 38.5 (CH2Ph), 37.0 (CH2CHdCH2).
(2S)-2-Cyclop en tylm eth yl-3-p h en yl-1-(th ien -2′-yl)-p r o-
p a n -1-on e 11m . Cleavage, after purification by flash chro-
matography on silica (eluting with 5% EtOAc/petroleum ether
(40-60 °C)), gave 11m (22.4 mg, 21%) as a yellow oil: m/z (EI+
mode) 298 (M+, 5), 216 (40), 215 (44), 111 (52), 91 (29), 85 (64),
83 (100) and 47 (19); HRMS calcd for M+, C19H22OS 298.1391,
found 298.1390; νmax (Golden Gate)/cm-1 3103w, 3082w, 3026w,
2933m, 2852w, 1641s (CdO), 1605w, 1516w; [R]D +62.4 (c )
(2R)-2-Bu tyl-1-(th ien -2-yl)p en t-4-en -1-on e 11p . Cleav-
age, after purification using flash chromatography on silica
(eluting with 5% EtOAc/petroleum ether (40-60 °C)), gave 11p
(24.3 mg, 32%) as a yellow oil: m/z (EI+ mode) 222 (M+, 2),
166 (15), 111 (59), 83 (100) and 47 (17); HRMS calcd for M+,
1
1.61 in CHCl3); H NMR (400 MHz, CDCl3) δ 7.51-7.50 (2H,
m, 2 × CH thiophene), 7.27-7.03 (5H, m, ArH), 6.99-6.96 (1H,
m, CH thiophene), 3.50-3.43 (1H, m, CHBn), 3.00 (1H, dd, J
) 8.0, 13.5, 1H of CH2Ph), 2.70 (1H, dd, J ) 6.3, 13.5 Hz, 1H,
of CH2Ph), 1.90-1.83 (1H, m, 1H of CH2), 1.72-1.62 (3H, m,
CH and CH2), 1.49-1.35 (5H, m, 2 × CH2 and 1H of CH2),
1.02-0.92 (2H, m CH2); 13C NMR (100 MHz, CDCl3) δ 197.2
(CdO), 145.5 (ArC), 140.1 (ArC), 134.2 (CH thiophene), 132.0
(CH thiophene), 129.3 (2 × ArCH), 128.7 (2 × ArCH), 128.5
(CH thiophene), 126.5 (ArCH), 50.3 (CHBn), 39.7 (CH2Ph), 39.4
(CHCH2), 38.6 (CH), 33.6 (CH2), 33.0 (CH2), 25.5 (2 × CH2).
(2R)-2-Cyclopen tylm eth yl-1-(th ien -2-yl)h exan -1on e 11n
a n d (2R)-2-Cyclop en tylm eth yl-1,1-d i(th ien -2-yl)h exa n -1-
ol 12. Cleavage, after purification by flash chromatography
on silica (eluting with 5% EtOAc/petroleum ether (40-60 °C)),
gave 11n (23.6 mg, 27%) as a yellow oil: m/z (EI+ mode) 264
(M+, 4), 208 (27), 182 (70), 139 (68), 111 (100), 83 (15), 55 (13)
and 41 (14); HRMS calcd for M+, C16H24OS 264.1548, found
264.1549; νmax (neat)/cm-1 2951s, 2858s, 1658s (CdO), 1518m,
C
13H18OS 222.1078, found 222.1077; νmax (neat/cm-1) 3077m
(CdC), 2929s, 1658s (CdO), 1415s, 993m (CdCH2), 914s (Cd
CH2); [R]D +6.27 (c ) 1.10 in CHCl3); 1H NMR (400 MHz,
CDCl3) δ 7.67 (1H, dd, J ) 1.1, 3.8 Hz, CH thiophene), 7.57
(1H, dd, J ) 1.1, 4.9 Hz, CH thiophene), 7.06 (1H, dd, J ) 3.8,
4.9 Hz, CH thiophene), 5.73-5.63 (1H, m, CH ) CH2), 5.00-
4.88 (2H, m, CH2dCH), 3.24-3.19 (1H, m, CH), 2.48-2.40 (1H,
m, 1H of CH2CHdCH2), 2.24-2.17 (1H, m, 1H of CH2CHd
CH2), 1.76-1.67 (1H, m, 1H of CHCH2), 1.53-1.44 (1H, m,
1H of CHCH2), 1.27-1.14 (4H, m, 2 × CH2), 0.78 (3H, t, J )
6.9 Hz, CH3); 13C NMR (100 MHz, CDCl3) δ 196.9 (CdO), 145.6
(C thiophene), 136.1 (CHdCH2), 134.2 (CH thiophene), 132.0
(CH thiophene), 128.6 (CH thiophene), 117.1 (CH2dCH), 48.6
(CH), 37.2 (CH2CHdCH2), 32.5 (CHCH2), 30.0 (CH2), 23.2
(CH2), 14.3 (CH3).
(2S)-2-Ben zyl-1-(th ien -2-yl)p en ta n -1-on e 11q. Cleavage,
after purification using flash chromatography on silica (eluting
with 5% EtOAc/petroleum ether (40-60 °C)), gave 11q (29.1
mg, 34%) as a yellow oil: m/z (EI+ mode) 258 (M+, 13), 215
1
1415s, 1236s; [R]D -14.3 (c ) 1.81 in CHCl3); H NMR (400
MHz, CDCl3) δ 7.66 (1H, dd, J ) 1.1, 3.8 Hz, CH thiophene),
7.56 (1H, dd, J ) 1.1, 4.9 Hz, CH thiophene), 7.07 (1H, dd, J
(43), 111 (49), 84 (100) and 49 (98); HRMS calcd for M+, C16H18
-
OS 258.1078, found 258.1080; νmax (neat/cm-1) 2929s, 1654s
1
(CdO), 1415s; [R]D +8.27 (c ) 1.15 in CHCl3); H NMR (400
(24) Meakin, B. J .; Mumford, F. R.; Ward, E. R. J . Pharm. Phar-
macol. 1959, 540.
(25) Felkin, H.; Swierczewski, G.; Tambute´, A. Tetrahedron Lett.
1969, 10, 707.
MHz, CDCl3) δ 7.52-7.50 (2H, m, 2 × CH thiophene), 7.18-
7.02 (5H, m, ArH), 6.98 (1H, apparent t, J ) 4.4 Hz, CH
thiophene), 3.46-3.39 (1H, m, CH), 3.02 (1H, dd, J ) 7.8, 13.6
J . Org. Chem, Vol. 69, No. 3, 2004 799