Notes
J . Org. Chem., Vol. 66, No. 5, 2001 1909
50.1, 30.3, 22.0, 20.9, 13.6; HRMS calcd for C10H14O3 (M + Na+)
205.0835, found 205.0843.
δ 0.95 (t, 3H, J ) 7.3 Hz), 1.50 (m, 2H), 2.96 (m, 4H), 3.47 (s,
2H), 4.72 (bs, 2H), 7-15-7.30 (m, 5H); 201.6, 166.7, 141.3, 140.8,
128.8, 128.6, 126.4, 88.4, 73.8, 54.0, 49.5, 45.5, 29.7, 22.08, 20.9,
13.6; HRMS calcd for C17H20O3 (M + Na+) 295.1306, found
295.1312.
Cin n am yl 3-oxo-4-pen ten oate (27): chromatography, EtOAc/
hexane 20:80 f 10:30; 1H NMR (250 MHz, CDCl3) δ 3.60 (s,
ketonic H at C(2)), 4.78 (d, J ) 5.9 Hz, 2H), 5.10 (s, enolic H at
C(2)), 5.50 (t, 1H), 5.94-6.36 (m 3H), 6.64 (d, J ) 15.7 Hz, 2H),
7.25-7.40 (m, 5H), 11.8 (s, enol OH); HRMS calcd for C14H14O3
(M + Na+) 253.0835, found 253.0846.
Ben zyl 2-oxocyclop en ta n eca r boxyla te (28): chromatog-
raphy, EtOAc/hexane 10:90 f 20:80; 1H NMR (250 MHz, CDCl3)
δ 1.81-1.90 (m, 1H), 2.10-2.14 (m, 1H), 2.2-2.4 (m, 4H), 3.21
(t, J ) 9.2 Hz, 1H), 5.18 (s, 2H), 7.36 (m, 5H); 13C NMR (125
MHz, CDCl3) δ 212.3, 169.5, 135.8, 128.8, 128.5, 128.3, 67.2, 55.0,
38.3, 27.6, 21.3; HRMS calcd for C13H14O3 (M + Na+) 241.0835,
found 241.0837.
MeO-P EG-3-oxobu ta n oa te (22). Poly(ethyleneglycol) mono-
methyl ether (Mw 5000) (5.0 g, 1 mmol) was dissolved in methyl
acetoacetate (10 mL, 80 mmol) and reacted with CALB (500 mg)
according to the general transesterification procedure. After 8
h, the reaction mixture was dissolved in THF (50 mL), filtered,
and precipitated into diethyl ether (800 mL) at 0 °C. The white
precipitate was collected to afford the product as a white solid
(4.98 g, 97%): 1H NMR (500 MHz, CDCl3) δ 2.24 (s, 3H), 3.34 (s,
3H), 3.45 (s, 2H), 3.50-3.70 (bs, 450H), 4.27 (t, J ) 7.1 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ 200.6, 167.3, 72.1, 70.8, 69.1, 64.5,
59.2, 50.2, 30.3.
Eth en yl 3-p h en ylp r op yl-3-oxobu ta n oa te (S)-(23): [R]25
D
) -3.7° (c ) 2.1, CH2Cl2), 90% ee; chromatography, EtOAc/
hexane 10:90 f 20:80; 1H NMR (500 MHz, CDCl3) δ 1.91-2.09
(m, 2H), 2.28 (s, 3H), 2.62-2.77 (m, 2H), 3.47 (s, 2H), 5.26 (d, J
) 10.6 Hz, 1H), 5.33 (d, J ) 12.5 Hz, 1H), 5.36 (m, 1H), 7.17-
7.25 (m, 3H), 7.27-7.34 (m, 2H); 13C NMR (125 MHz, CDCl3) δ
200.6, 166.5, 141.3, 135.9, 128.6, 128.5, 126.2, 117.7, 75.6, 50.4,
35.8, 31.5, 30.3; HRMS calcd for C15H18O3 (M + Na+) 269.1148,
found 269.1155.
Met h yl 3-p h en ylp r op -2-en yl-3-oxob u t a n oa t e ((R)-33):
[R]25 ) +81.1° (c ) 1.1, CH2Cl2), 93% ee; chromatography,
D
EtOAc/hexane 10:90 f 40:60; 1H NMR (250 MHz, CDCl3) δ 1.40
(d, J ) 6.6 Hz, 2H), 2.23 (s, 3H), 3.42 (s, 2H), 5.55 (m, 1H), 6.21-
(dd, J ) 15.9, 6.6 Hz, 1H), 6.58 (d, J ) 16.1 Hz, 1H), 7.21-7.39
(m, 5H); 13C NMR (125 MHz, CDCl3) δ 200.7, 166.6, 136.4, 132.4,
128.8, 128.4, 128.3, 126.8, 72.6, 50.6, 30.3, 20.5; HRMS calcd
for C14H16O3 (M + Na+) 255.0992, found 255.1004.
Meth yl 3-(4-h yd r oxyp h en yl)p r op yl-3-oxobu ta n oa te (24):
chromatography, EtOAc/hexane 10:90 f 50:50; 1H NMR (250
MHz, CDCl3) δ 2.72 (d, J ) 6.6 Hz, 3H), 1.77-1.90 (m, 1H),
1.91-1.97 (m, 1H), 2.28 (s, 3H), 2.52-2.69 (m, 2H), 3.33 (s, 2H),
4.99 (m, 1H), 6.75 (d, J ) 7.8 Hz, 2H), 7.02 (d, J ) 7.8 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ 201.3, 167.2, 154.2, 133.6, 129.7,
115.6, 77.2, 50.7, 37.9, 31.02, 30.5, 20.2; HRMS calcd for
C14H18O4 (M + Na+) 273.1097, found 273.1094.
Ack n ow led gm en t. This work was supported by the
National Institutes of Health (GM56154) and the
Skaggs Institute for Chemical Biology. A.C. acknowl-
edges a fellowship from the Wennergren Foundations,
Sweden. The provision of enzyme by Novo Nordisk A/S,
Denmark, is also gratefully acknowledged.
Cin n a m yl 3-oxo-5-p h en ylp en ta n oa te (25): chromatogra-
1
phy, EtOAc/hexane 20:80 f 10:30; H NMR (250 MHz, CDCl3)
δ 2.82-3.05 (m, 4H), 4.79 (d, J ) 6.2 Hz, 2H), 6.23 (m, 1H), 6.64
(d, J ) 15.8 Hz, 1H), 7.20-7.42 (m, 10H); 13C NMR (125 MHz,
CDCl3) δ 201.8, 167.0, 140.7, 136.2, 135.1, 128.8, 128.7, 128.5,
126.9, 126.4, 122.7, 66.1, 49.6, 44.7, 29.6; HRMS calcd for
Su p p or t in g In for m a t ion Ava ila b le: 1H NMR and 13C
NMR spectra of 22-24, 28, and 33. This material is available
C
20H20O3 (M + Na+) 331.1305, found 331.1305.
Hex-2-yn yl 5-p h en yl-3-oxop en ta n oa te (26): chromatogra-
1
phy, EtOAc/hexane 10:40 f 10:30; H NMR (250 MHz, CDCl3)
J O001478O