Stecko et al.
1H NMR (500 MHz, C6D6) δ 7.30-7.00 (5H, Ph), 4.32 (1H, d, J
11.4 Hz), 4.23 (1H, m), 4.08 (1H, d, J 11.4 Hz), 3.67-3.60 (2H,
H-2a), 3.50 (1H, dq, J 8.5, 6.1 Hz), 3.21 (1H, dd, J 8.5, 5.9 Hz),
2.79 (1H, m), 1.69 (1H, m), 1.57 (1H, m), 1.22 (3H, d, J 6.1 Hz),
0.99 (9H, s); 13C NMR (125 MHz, C6D6, without Ph carbon atoms)
δ 178.1, 73.8, 71.7, 71.0, 70.2, 64.3, 58.2, 45.7, 39.5, 28.4, 18.2;
IR (film) 17601 cm-1; HR MS (ESI) calcd for C19H27NO3Na [M
+ Na+] 340.1883, found 340.1882; HPLC hexane/2-propanol 95/
5, flow 1 mL/min, tR 5.5 min. Anal. Calcd for C19H27NO3: C, 71.89;
H, 8.57; N, 4.41. Found: C, 71.87; H, 8.56; N, 4.40.
(4R,5S,6R,4′S)-4-tert-Butoxy-6-(2′,2′-dimethyl-1′,3′-dioxolan-
4′-yl)-1-azabicyclo[3.2.0]heptan-7-one (13a): colorless oil; [R]D
1
+8.3 (c 1.40, CH2Cl2); H NMR (500 MHz, C6D6) δ 4.52 (1H,
m), 4.08 (1H, dd, J 9.8, 7.8 Hz), 3.96 (1H, ddd, J 9.8, 5.8, 2.0 Hz),
3.64 (1H, dd, J 7.8, 5.8 Hz), 3.54 (1H, ddd, J 14.2, 8.1, 5.3 Hz),
3.44 (1H, dd, J 5.6, 3.9 Hz), 2.84 (1H, dd, J 5.6, 2.0 Hz), 2.76
(1H, m), 2.09 (1H, m), 1.67 (1H, m), 1.49 (3H, s), 1.32 (3H, s),
1.10 (9H, s); 13C NMR (125 MHz, C6D6) δ 175.4, 110.3, 73.6,
72.7, 71.2, 67.8, 62.7, 51.8, 44.6, 38.9. 28.5, 26.9, 26.2; IR (film)
1766 cm-1; HR MS (ESI) calcd for C15H25NO4Na [M + Na+]
306.1676, found 306.1683. Anal. Calcd for C15H25NO4: C, 63.58;
H, 8.89; N, 4.94. Found: C, 63.56; H, 8.90; N, 4.93.
(4S,5R,6S,1′R)-4-tert-Butoxy-6-(1′-tert-butyldiphenylsilyloxy)-
benzyl-1-azabicyclo[3.2.0]heptan-7-one (10a): colorless oil; [R]D
1
(3R,5S,6S,4′S)-4-tert-Butoxy-6-(2′,2′-dimethyl-1′,3′-dioxolan-
-15.7 (c 3.6, CH2Cl2); H NMR (500 MHz, C6D6) δ 8.10-7.20
4′-yl)-1-azabicyclo[3.2.0]heptan-7-one (14): colorless oil; [R]D
(15H, m), 4.73 (1H, d, J 10.4 Hz), 4.07 (1H, dd, J 10.4 Hz, 6.5
Hz), 3.71 (1H, br dd, J 11.6, 7.1 Hz), 3.59 (1H, br d, J 5.4 Hz),
3.39 (1H, d, J 6.5 Hz), 2.75 (1H, ddd, J 11.6, 11.4, 5.3 Hz),
1.34-1.26 (2H, m), 1.24 (9H, s), 1.09 (9H, s); 13C NMR (125 MHz,
C6D6, without Ph carbon atoms) δ 179.4, 73.6, 72.7, 70.4, 63.4,
58.5, 45.9, 38.9, 27.8, 27.3, 19.7. 19.2; IR (film) 1758 cm-1; HR
MS (ESI) calcd for C33H41NO3NaSi [M + Na+] 550.2753, found
550.2751; HPLC hexane/2-propanol 98/2, flow 1 mL/min, tR 5.9
min. Anal. Calcd for C33H41NO3Si: C, 75.10; H, 7.83; N, 2.65.
Found: C, 75.07; H, 7.84; N, 2.63.
1
-123.2 (c 0.6, CH2Cl2); H NMR (500 MHz, C6D6) δ 4.11 (1H,
dd, J 8.2, 6.0 Hz), 4.06 (1H, ddd, J 10.0, 6.0, 5.9 Hz), 3.99 (1H,
m), 3.82 (1H, d, J 8.2, 5.9 Hz), 3.76 (1H, m), 3.65 (1H, d, J 11.8,
5.8 Hz), 3.15 (1H, dd, J 10.0, 5.3 Hz), 2.60 (1H, dd, J 11.8, 3.6
Hz), 1.74-1.69 (2H, m), 1.30 (3H, s), 1.24 (3H, s), 0.91 (9H, s);
13C NMR (125 MHz, C6D6) δ 175.6, 109.1, 75.8, 73.5, 71.9, 68.6,
55.1, 54.4, 53.83, 35.1, 28.1, 27.1, 25.7; IR (film) 1758 cm-1; HR
MS (ESI) calcd for C15H25NO4Na [M + Na+] 306.1676, found
306.1661. Anal. Calcd for C15H25NO4: C, 63.58; H, 8.89; N, 4.94.
Found: C, 63.54; H, 8.86; N, 4.90.
(4S,5R,6R,1′R)-4-tert-Butoxy-6-(1′-tert-butyldiphenylsilyloxy)-
benzyl-1-azabicyclo[3.2.0]heptan-7-one (10b). The sample con-
tained inseparable impurities (purity ∼90% according to HPLC):
(3S,5S,6S,4′S)-4-tert-Butoxy-6-(2′,2′-dimethyl-1′,3′-dioxolan-
4′-yl)-1-azabicyclo[3.2.0]heptan-7-one (15a): colorless oil; [R]D
1
-103.6 (c 0.38, CH2Cl2); H NMR (500 MHz, C6D6) δ 4.61 (1H,
1
colorless oil; H NMR (500 MHz, C6D6, without protons of Ph
ddd, J 10.0, 8.5, 7.7 Hz), 4.22 (1H, dd, J 7.7, 6.1 Hz), 3.99 (1H,
dd, J 8.5, 6.1 Hz), 3.74 (1H, dddd, J 5.6, 4.7, 4.4, 2.8 Hz), 3.52
(1H, dd, J 12.0, 2.8 Hz), 3.45 (1H, dt, J 8.0, 5.3 Hz), 3.32 (1H, dd,
J 10.0, 5.3 Hz), 2.45 (1H, dd, J 12.0, 4.7 Hz), 1.87 (1H, ddd, J
14.1, 5.3, 4.4 Hz), 1.64 (1H, ddd, J 14.1, 8.0, 5.6 Hz), 1.40 (3H,
s), 1.27 (3H, s), 0.91 (9H, s); 13C NMR (125 MHz, C6D6) δ 176.2,
108.7, 75.7, 73.7, 72.2, 68.6, 57.4, 54.7, 54.2, 34.7, 28.1, 27.2, 25.8;
IR (film) 1760 cm-1; HR MS (ESI) calcd for. C15H25NO4Na [M +
Na+] 306.1676, found 306.1677. Anal. Calcd for C15H25NO4: C,
63.58; H, 8.89; N, 4.94. Found: C, 63.55; H, 8.87; N, 4.95.
(3S,5R,6R,4′S)-4-tert-Butoxy-6-(2′,2′-dimethyl-1′,3′-dioxolan-
4′-yl)-1-azabicyclo[3.2.0]heptan-7-one (15b): colorless oil; [R]D
groups) δ 7.05 (1H, br s), 6.88 (1H, d, J 1.5 Hz), 4.39 (1H, dd, J
3.6, 1.5 Hz), 3.76 (1H, m), 3.62 (1H, ddd, J 11.6, 7.3, 4.9 Hz),
2.90 (1H, m) 1.64-1.52 (2H, m), 1.26 (9H, s), 0.92 (9H, s); IR
(film) 1745 cm-1; HR MS (ESI) calcd for C28H39NO3NaSi [M +
Na+] 488.2591, found 488.2611; HPLC hexane/2-propanol 95/5,
flow 1 mL/min, tR 4.8 min.
(4R,5S,6R,1′R)-4-tert-Butoxy-6-(tert-butyldiphenylsilyloxy)-
benzyl-1-azabicyclo[3.2.0]heptan-7-one (11): colorless oil; [R]D
+344.1 (c 0.25, CH2Cl2); 1H NMR (500 MHz, C6D6) δ 8.00-6.80
(15H, m), 5.37 (1H, d, J 3.3 Hz), 4.98 (1H, m), 3.76 (1H, ddd, J
11.5, 7.9, 3.2 Hz), 3.65 (1H, dd, J 6.1, 2.4 Hz), 3.48 (1H, dd, J
6.1, 3.3 Hz), 2.86 (1H, ddd, J 11.5, 9.2, 6.5 Hz), 2.15 (1H, m),
1.73 (1H, m), 1.19 (9H, s), 1.08 (9H, s); 13C NMR (125 MHz,
C6D6, without Ph carbon atoms) δ 177.6, 74.0, 73.8, 71.5, 64.7,
59.7, 45.3, 39.8, 28.9, 27.4, 19.7; IR (film) 1759 cm-1; HR MS
(ESI) calcd for C33H41NO3NaSi [M + Na+] 550.2748, found
550.2730; HPLC hexane/2-propanol 95/5, flow 1 mL/min, tR 6.3
min. Anal. Calcd for C33H41NO3Si: C, 75.10; H, 7.83; N, 2.65.
Found: C, 75.05; H, 7.80; N, 2.67.
(4S,5R,6S,4′S)-4-tert-Butoxy-6-(2′,2′-dimethyl-1′,3′-dioxolan-
4′-yl)-1-azabicyclo[3.2.0]heptan-7-one (12): colorless oil; [R]D
-77.5 (c 0.78, CH2Cl2); 1H NMR (500 MHz, C6D6) δ 4.15 (1H,
ddd, J 6.3, 2.7, 2.2 Hz), 4.04 (1H, dd, J 8.5, 6.0 Hz), 3.88 (1H,
ddd, J 10.1, 6.0, 5.8 Hz), 3.77 (1H, dd, J 8.5, 6.0 Hz), 3.60
(1H, dd, J 5.7, 2.2 Hz), 3.54 (1H, ddd, J 11.8, 7.5, 3.1 Hz),
3.16 (1H, dd, J 10.1, 5.7 Hz), 2.75 (1H, ddd, J 11.6, 9.84, 6.9
Hz), 1.70-1.58 (2H, m), 1.28 (3H, s), 1.19 (3H, s), 1.11 (9H,
s); 13C NMR (125 MHz, C6D6) δ 176.4, 109.1, 74.0, 71.8, 70.7,
68.7, 63.1, 55.5, 45.6, 39.5, 28.3, 27.0, 25.5; IR (film) 1763
cm-1; HR MS (ESI) calcd for C15H25NO4Na [M + Na+]
306.1676, found 306.1681; HPLC hexane/2-propanol 95/5, flow
1 mL/min, tR 16 min. Anal. Calcd for C15H25NO4: C, 63.58; H,
8.89; N, 4.94. Found: C, 63.56; H, 8.88; N, 4.93.
1
+20.2 (c 1.5, CH2Cl2); H NMR (500 MHz, C6D6) δ 4.30 (1H,
dq, J 7.2, 6.2 Hz), 4.01 (1H, dd, J 9.3, 7.8 Hz), 3.84 (1H, dd, J
11.7, 6.3 Hz), 3.70 (1H, ddd, J 9.3, 5.9, 2.2 Hz), 3.60 (1H, dd,
J 7.8, 5.9 Hz), 3.44 (1H, ddd, J 8.2, 5.8, 4.7 Hz), 2.76 (1H, dd,
J 5.8, 2.2 Hz), 2.61 (1H, dd, J 11.7, 6.2 Hz), 2.23 (1H, ddd, J
14.3, 7.2, 4.7 Hz), 1.58 (1H, ddd, J 14.3, 8.2, 6.2 Hz), 1.51
(3H, s), 1.33 (3H, s), 1.03 (9H, s); 13C NMR (125 MHz, C6D6)
δ 175.9, 110.2, 74.6, 73.4, 72.4, 67.8, 54.1, 53.4, 53.3, 34.4,
28.1, 27.1, 26.3; IR (film) 1759 cm-1; HR MS (ESI) calcd for
C15H25NO4Na [M + Na+] 306.1676, found 306.1680. Anal.
Calcd for C15H25NO4: C, 63.58; H, 8.89; N, 4.94. Found: C,
63.59; H, 8.90; N, 4.92.
Acknowledgment. Financial support for this work was
provided through the Polish Ministry of Science and Higher
Education Grant No. N N204 156036.
Supporting Information Available: 1H and 13C NMR
spectra of 5-15; NOE experiments for 12 and 13a. This material
JO900121X
3100 J. Org. Chem. Vol. 74, No. 8, 2009