2
46
4
-Methylcyclohexylcarbonyloxymethyl (1R,5S,6S)-6-
m), 2.19 (2H, d, Jꢁ6.9 Hz), 3.10 (1H, quint, Jꢁ7.3 Hz),
3.15 (1H, dd, Jꢁ2.3, 6.9 Hz), 3.28 (1H, br s), 3.31 (2H, t,
Jꢁ7.6 Hz), 3.87ꢀ3.91 (2H, m), 3.94 (2H, t, Jꢁ7.6 Hz),
4.04ꢀ4.16 (3H, m), 4.30ꢀ4.37 (2H, m), 5.79 (1H, d,
Jꢁ5.6 Hz), 5.85 (1H, d, Jꢁ5.6 Hz); HRMS (EI) calcd for
[(R)-1-hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)-
azetidin-3-yl]thio-1-carbapen-2-em-3-carboxylate (11)
Amorphous powder (80% yield), mp 78ꢀ79°C; IR (KBr)
cm 3382, 2928, 1774, 1615, 1545; H-NMR (270 MHz,
CDCl ) d 0.88 (0.9H, d, Jꢁ6.6 Hz), 0.89 (2.1H, d,
ꢀ1
1
ꢂ
C H N O S 537.1967, found m/z 537.1992 (M) .
3
25 35
3
6 2
Jꢁ6.6 Hz), 1.22 (3H, d, Jꢁ7.3 Hz), 1.34 (3H, d, Jꢁ6.3 Hz),
1
.34ꢀ1.80 (7H, m), 1.96ꢀ2.05 (2H, m), 2.23ꢀ2.28 (0.3H,
Cyclohexylcarbonyloxymethyl (1R,5S,6S)-6-[(R)-1-
hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)azetidin-
3-yl]thio-1-carbapen-2-em-3-carboxylate (15)
m), 2.45 (1H, br s), 2.57ꢀ2.59 (0.7H, m), 3.15ꢀ3.21 (1H,
m), 3.23 (1H, dd, Jꢁ2.3, 6.6 Hz), 3.40 (2H, t, Jꢁ7.6 Hz),
4
.00ꢀ4.05 (4H, m), 4.15ꢀ4.27 (3H, m), 4.43ꢀ4.51 (2H,
m), 5.86 (0.3H, d, Jꢁ5.6 Hz), 5.87 (0.7H, d, Jꢁ5.6 Hz),
.94 (0.3H, d, Jꢁ5.6 Hz), 5.95 (0.7H, d, Jꢁ5.6 Hz); HRMS
EI) calcd for C H N O S 537.1967, found m/z 537.1974
Colorless crystals (71% yield from AcOEt), mp
ꢀ1
120ꢀ122°C; IR (KBr) cm 3195, 2931, 1785, 1695, 1611,
1
5
1541; H-NMR (270 MHz, CDCl ) d 1.31 (3H, d,
3
(
(
Jꢁ7.3 Hz), 1.41 (3H, d, Jꢁ6.3 Hz), 1.31ꢀ1.73 (6H, m),
1.81ꢀ1.85 (2H, m), 1.99ꢀ2.13 (2H, m), 2.40ꢀ2.51 (1H,
m), 2.99 (1H, br s), 3.12ꢀ3.18 (1H, m), 3.20ꢀ3.27 (1H,
m), 3.47 (2H, t, Jꢁ7.6 Hz), 4.03ꢀ4.13 (4H, m), 4.16ꢀ4.34
(3H, m), 4.51 (2H, t, Jꢁ7.6 Hz), 5.93 (1H, d, Jꢁ5.6 Hz),
6.03 (1H, d, Jꢁ5.6 Hz); HRMS (EI) calcd for
2
5
35
3
6 2
ꢂ
M) .
1
-(Cyclohexyloxycarbonyloxy)ethyl (1R,5S,6S)-6-[(R)-1-
hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)azetidin-
-yl]thio-1-carbapen-2-em-3-carboxylate (12)
Amorphous powder (82% yield, diastereo-mixture), mp
3
ꢂ
C H N O S 523.1811, found m/z 523.1791 (M) ; Anal.
2
4
33
3
6 2
ꢀ1
1
07ꢀ109°C; IR (KBr) cm 3184, 2937, 1790, 1611, 1548;
Calcd for C H N O S : C, 55.05; H, 6.35; N, 8.02. Found:
24 33 3 6 2
C, 55.00; H, 6.33; N, 7.91.
1
H-NMR (270 MHz, CDCl ) d 1.20ꢀ1.95 (19H, m),
3
3
.12ꢀ3.23 (2H, m), 3.36 (2H, t, Jꢁ7.6 Hz), 3.92ꢀ4.03
(
4
4H, m), 4.10ꢀ4.23 (3H, m), 4.34ꢀ4.42 (2H, m),
.63ꢀ4.69 (1H, m), 6.88 (1H, q, Jꢁ2.6 Hz); HRMS (FAB)
(5-Methyl-2-oxo-1,3-dioxolen-4-yl)methyl (1R,5S,6S)-6-
[(R)-1-hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)-
azetidin-3-yl]thio-1-carbapen-2-em-3-carboxylate (16)
Amorphous powder (54% yield), mp 115°C (decomp.); IR
calcd for C H N O S 554.1995, found m/z 554.1964
2
5
36
3
7 2
ꢂ
(MꢂH) ; Anal. Calcd for C H N O S : C, 54.23; H, 6.37;
25 35 3 7 2
ꢀ1
1
N, 7.59. Found: C, 53.72; H, 6.27; N, 7.99.
(KBr) cm 3382, 2969, 1820, 1767, 1610, 1457; H-NMR
(
270 MHz, CDCl ) d 1.22 (3H, d, Jꢁ7.3 Hz), 1.34 (3H, d,
3
1
-Methylcyclohexylcarbonyloxymethyl (1R,5S,6S)-6-
Jꢁ6.3 Hz), 2.22 (3H, s), 2.46 (1H, br s), 3.14ꢀ3.26 (2H,
m), 3.39ꢀ3.45 (2H, m), 4.00ꢀ4.09 (4H, m), 4.13ꢀ4.28
(3H, m), 4.47ꢀ4.56 (2H, m), 4.98 (1H, d, Jꢁ3.9 Hz), 5.05
(1H, d, Jꢁ3.9 Hz); HRMS (FAB) calcd for C H N O S
[(R)-1-hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)-
azetidin-3-yl]thio-1-carbapen-2-em-3-carboxylate (13)
Colorless crystals (88% yield from MeCN), mp
2
1
26
3
7 2
ꢀ1
ꢂ
1
37ꢀ139°C; IR (KBr) cm 3123, 2940, 1790, 1747, 1717,
496.1212, found m/z 496.1240 (MꢂH) .
1
1
613 1550; H-NMR (270 MHz, CDCl ) d 1.13ꢀ1.54 (8H,
3
m), 1.19 (3H, s), 1.22 (3H, d, Jꢁ7.3 Hz), 1.33 (3H, d,
Jꢁ6.3 Hz), 2.02ꢀ2.11 (2H, m), 2.41 (1H, br s), 3.13ꢀ3.25
1,3-Dihydro-3-oxo-1-isobenzofuranyl (1R,5S,6S)-6-[(R)-
1-hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)-
azetidin-3-yl]thio-1-carbapen-2-em-3-carboxylate (17)
(
4
2H, m), 3.39 (2H, t, Jꢁ7.6 Hz), 3.97ꢀ4.05 (4H, m),
.11ꢀ4.26 (3H, m), 4.42ꢀ4.49 (2H, m), 5.87 (1H, d,
Amorphous powder (84% yield), mp 120°C (decomp.); IR
ꢀ
1
1
Jꢁ5.6 Hz), 5.97 (1H, d, Jꢁ5.6 Hz); HRMS (FAB) calcd for
(KBr) cm 3421, 2969, 1782, 1611, 1541; H-NMR
ꢂ
C H N O S 538.2046, found m/z 538.2032 (MꢂH) ;
(270 MHz, CDCl ) d 1.21 (1.5H, d, Jꢁ7.3 Hz), 1.24 (1.5H,
2
5
36
3
6
2
3
Anal. Calcd for C H N O S : C, 55.84; H, 6.56; N, 7.81.
Found: C, 55.52; H, 6.47; N, 7.65.
d, Jꢁ6.9 Hz), 1.29 (3H, d, Jꢁ6.3 Hz), 2.74 (1H, br s),
3.18ꢀ3.28 (2H, m), 3.34ꢀ3.41 (2H, m), 3.94ꢀ4.04 (4H,
m), 4.10ꢀ4.26 (3H, m), 4.39ꢀ4.49 (2H, m), 7.45 (0.5H, s),
7.51 (0.5H, s), 7.61ꢀ7.79 (3H, m), 7.89ꢀ7.94 (1H, m);
HRMS (FAB) calcd for C H N O S 516.1263, found m/z
2
5
35
3
6 2
Cyclohexylacetoxymethyl (1R,5S,6S)-6-[(R)-1-
hydroxyethyl]-1-methyl-2-[1-(1,3-thiazolin-2-yl)azetidin-
2
4
26
3
6 2
ꢂ
3-yl]thio-1-carbapen-2-em-3-carboxylate (14)
516.1274 (MꢂH) .
Amorphous powder (76% yield), mp 70ꢀ71°C; IR (KBr)
ꢀ1
1
cm 3381, 2925, 1771, 1615, 1542; H-NMR (270 MHz,
CDCl ) d 0.81ꢀ1.00 (2H, m), 1.00ꢀ1.26 (3H, m), 1.15
3
(3H, d, Jꢁ7.3 Hz), 1.25 (3H, d, Jꢁ6.3 Hz), 1.55ꢀ1.80 (6H,