The Journal of Organic Chemistry
Page 4 of 7
detector and HP-5 capillary column (polydimethylsiloxane with 5 %
172.8, 137.8, 129.5, 128.6, 126.7, 69.1, 60.8, 43.0, 40.6, 14.2. GC-MS
(EI, 70 eV): m/z (%) = 190(32), 145(20), 117(100), 91(74), 71(30).
HRMS (ESI-TOF) calcd for C12H16O3 [M + Na]+: 231.0991, Found:
231.0996.
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phenyl groups, 30 m, 0.32 mm i.d., 0.25 μm film thickness) using argon
as carrier gas. All of the reagents were purchased from Sigma-Aldrich,
Alfa-Aesar, Acros, TCI, and used without further purification.
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General Procedures. A 4 mL screw-cap vial was charged with
CoBr2 (10.9 mg, 2.5 mol%), Mn powder (~ 325 mesh) (16.5 mg, 15
mol%), pyrazole (13.6 mg, 10 mol%) and an oven-dried stirring bar.
The vial was closed by Teflon septum and phenolic cap and connected
with atmosphere with a needle. After flashed the vials with argon and
vacuum three times, Absolute ethanol (2 mL) and 1, 2-epoxybutane (2
mmol) were injected by syringe. The vial was fixed in an alloy plate and
put into Paar 4560 series autoclave (500 mL) under argon atmosphere.
At room temperature, the autoclave is flushed with carbon monoxide
for three times and 40 bar of carbon monoxide was charged. The
autoclave was reacted at 60°C for 20 hours. Afterwards, the pressure
was carefully released. After removal of solvent under reduced pressure,
pure product was obtained by column chromatography.
Ethyl 3-hydroxy-5-phenylpentanoate (3g).17b 418.1 mg, 94% yield,
colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.32 – 7.23 (m, 2H), 7.23
– 7.14 (m, 3H), 4.16 (q, J = 7.1 Hz, 2H), 4.07 – 3.95 (m, 1H), 3.13 (d,
J = 3.8 Hz, 1H), 2.88 – 2.77 (m, 1H), 2.75 – 2.64 (m, 1H), 2.50 (dd, J =
16.5, 3.6 Hz, 1H), 2.43 (dd, J = 16.5, 8.5 Hz, 1H), 1.90 – 1.79 (m, 1H),
1.78 – 1.68 (m, 1H), 1.26 (t, J = 7.2 Hz, 3H). 13C{1H} NMR (101
MHz, CDCl3) δ 173.1, 141.8, 128.5, 128.5, 125.9, 67.3, 60.8, 41.4, 38.2,
31.8, 14.2. GC-MS (EI, 70 eV): m/z (%) = 220(1), 204(25), 159(10),
130(83), 117(32), 91(100). HRMS (ESI-TOF) calcd for C13H18O3
[M + Na]+: 245.1148, Found: 245.1151.
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Ethyl 3-hydroxyhept-6-enoate (3h).9a 247.3 mg, 72% yield, colorless
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oil. H NMR (300 MHz, CDCl3) δ 5.91 – 5.65 (m, 1H), 5.00 (d, J =
17.1 Hz, 1H), 4.93 (d, J = 10.2 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 4.03
– 3.93 (m, 1H), 3.05 (s, 1H), 2.46 (dd, J = 16.3, 3.7 Hz, 1H), 2.37 (dd,
J = 16.3, 8.5 Hz, 1H), 2.25 – 1.98 (m, 2H), 1.75 – 1.38 (m, 2H), 1.23
(t, J = 7.1 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 172.9, 138.1,
115.0, 67.4, 60.7, 41.4, 35.6, 29.8, 14.2. GC-MS (EI, 70 eV): m/z (%) =
171(1), 154(25), 143(8), 130(33), 117(100), 109(40), 81(100),
71(99). HRMS (ESI-TOF) calcd for C9H16O3 [M + Na]+: 195.0977,
Found: 195.1003.
Analytic data. Ethyl 3-hydroxypentanoate (3a).9a 264.4 mg, 90%
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yield, colorless oil. H NMR (300 MHz, CDCl3) δ 4.14 (q, J = 7.1 Hz,
2H), 3.97 – 3.82 (m, 1H), 3.09 (s, 1H), 2.48 (dd, J = 16.3, 3.4 Hz, 1H),
2.36 (dd, J = 16.3, 8.9 Hz, 1H), 1.59 – 1.39 (m, 2H), 1.24 (t, J = 7.1 Hz,
3H), 0.93 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ
173.2, 69.4, 60.7, 41.0, 29.5, 14.2, 9.9. GC-MS (EI, 70 eV): m/z (%) =
145(5), 128(10), 117(100), 101(25), 89(40), 71(70). HRMS (ESI-
TOF) calcd for C7H14O3 [M + Na]+: 169.0835, Found: 169.0838.
Ethyl 3-hydroxybutanoate (3b).9a 243.9 mg, 92% yield, colorless oil.
1H NMR (300 MHz, CDCl3) δ 4.26 – 3.98 (m, 3H), 3.03 (s, 1H), 2.60
– 2.22 (m, 2H), 1.25 (d, J = 7.1 Hz, 2H), 1.25 – 1.15 (m, 3H). 13C{1H}
NMR (75 MHz, CDCl3) δ 172.9, 64.3, 60.7, 42.9, 22.5, 14.2. GC-MS
(EI, 70 eV): m/z (%) = 131(2), 117(70), 87(75), 71(65), 60(55),
43(100).
Ethyl 3-hydroxyheptanoate (3c).9a 290.3 mg, 83% yield, colorless oil.
1H NMR (400 MHz, CDCl3) δ 4.12 (q, J = 7.1 Hz, 2H), 3.99 – 3.92
(m, 1H), 3.00 (s, 1H), 2.45 (dd, J = 16.3, 3.3 Hz, 1H), 2.35 (dd, J =
16.3, 8.9 Hz, 1H), 1.56 – 1.26 (m, 6H), 1.23 (t, J = 7.1 Hz, 3H), 0.86 (t,
J = 7.1 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 173.1, 68.1, 60.7,
41.5, 36.3, 27.7, 22.6, 14.2, 14.1. GC-MS (EI, 70 eV): m/z (%) =
174(1), 156(5), 127(10), 117(100), 88(35), 71(55). HRMS (ESI-
TOF) calcd for C9H18O3 [M + Na]+: 197.1148, Found: 197.1151.
Ethyl 3-hydroxynonanoate (3d).17a 380.9 mg, 94% yield, colorless oil.
1H NMR (300 MHz, CDCl3) δ 4.14 (q, J = 7.1 Hz, 2H), 4.04 – 3.88
(m, 1H), 2.92 (s, 1H), 2.47 (dd, J = 16.3, 3.4 Hz, 1H), 2.36 (dd, J =
16.3, 8.8 Hz, 1H), 1.58 – 1.10 (m, 13H), 0.92 – 0.76 (m, 3H). 13C{1H}
NMR (75 MHz, CDCl3) δ 173.2, 68.1, 60.7, 41.4, 36.6, 31.9, 29.3,
25.5, 22.7, 14.2, 14.1. GC-MS (EI, 70 eV): m/z (%) = 201(1), 184(2),
155(3), 139(10), 117(100), 97(10), 89(25), 71(35). HRMS (ESI-
TOF) calcd for C11H22O3 [M + Na]+: 225.1461, Found: 225.1467.
Ethyl 7-acetoxy-3-hydroxyheptanoate (3i).17c 292.7 mg, 63% yield,
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colorless oil. H NMR (300 MHz, CDCl3) δ 4.14 (q, J = 7.1 Hz, 2H),
4.06 – 3.90 (m, 1H), 3.61 (t, J = 6.1 Hz, 2H), 3.28 (s, 1H), 2.48 (dd, J =
16.3, 3.8 Hz, 1H), 2.39 (dd, J = 16.3, 8.5 Hz, 1H), 2.18 (s, 1H), 1.65 –
1.36 (m, 6H), 1.25 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (75 MHz,
CDCl3) δ 173.1, 68.0, 62.6, 60.8, 41.5, 36.2, 32.4, 21.7, 14.3. GC-MS
(EI, 70 eV): m/z (%) = 170(2), 142(5), 127(15), 117(100), 85(45),
71(50), 43(30). HRMS (ESI-TOF) calcd for C9H18O4 [M + Na]+:
213.1103, Found: 213.1111.
Ethyl 3-hydroxy-4-(2,2,3,3-tetrafluoropropoxy)butanoate (3j). 389.9
mg, 74% yield, colorless oil. 1H NMR (300 MHz, CDCl3) δ 6.21 – 5.61
(m, 1H), 4.20 (dd, 1H), 4.18 – 4.12 (m, 2H), 3.89 (t, J = 12.6 Hz, 2H),
3.66 – 3.54 (m, 2H), 2.99 (s, 1H), 2.51 (d, J = 6.2 Hz, 2H), 1.26 (t, J =
7.1 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 172.2, 115.1 (t, J =
26.9 Hz), 109.3 (tt, J = 249.4, 34.8 Hz), 75.6, 68.5 (t, J = 28.2 Hz),
67.2, 61.0, 37.8, 14.2. 19F NMR (282 MHz, CDCl3) δ -121.73 – -
126.92 (m), -139.50 (d, J = 53.1 Hz). GC-MS (EI, 70 eV): m/z (%) =
263(1), 244(5), 217(30), 199(8), 175(65), 145(15), 117(100),
89(36), 71(80). HRMS (ESI-TOF) calcd for C9H14O4F4 [M + Na]+:
285.0726, Found: 285.0735.
Ethyl 3-hydroxy-4-phenoxybutanoate (3k).9a 156.4 mg, 35%
yield(CoBr2 as catalyst); 312.8 mg, 70% yield(CoCl2 as catalyst),
colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.33 – 7.23 (m, 2H), 7.00
– 6.85 (m, 3H), 4.49 – 4.36 (m, 1H), 4.19 (q, J = 7.1 Hz, 2H), 4.00 (d,
J = 5.3 Hz, 2H), 3.16 (s, 1H), 2.76 – 2.68 (m, 1H), 2.67 – 2.59 (m,
1H), 1.28 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ
172.2, 158.5, 129.6, 121.3, 114.7, 70.7, 66.9, 61.0, 38.2, 14.3. GC-MS
(EI, 70 eV): m/z (%) = 224(12), 206(23), 179(10), 161(35),
131(100), 103(75), 94(86), 85(35), 77(57). HRMS (ESI-TOF) calcd
for C12H16O4 [M + Na]+: 247.0941, Found: 247.0949.
Ethyl 3-hydroxytridecanoate (3e). 460.6 mg, 89% yield, colorless oil.
1H NMR (300 MHz, CDCl3) δ 4.15 (q, J = 7.1 Hz, 2H), 4.06 – 3.88
(m, 1H), 2.98 (s, 1H), 2.48 (dd, J = 16.4, 3.3 Hz, 1H), 2.37 (dd, J =
16.4, 8.8 Hz, 1H), 1.58 – 1.37 (m, 3H), 1.32 – 1.20 (m, 18H), 0.86 (t, J
= 6.6 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 173.2, 68.1, 60.7,
41.4, 36.6, 32.0, 29.7, 29.7, 29.7, 29.6, 29.4, 25.6, 22.8, 14.3, 14.2. GC-
MS (EI, 70 eV): m/z (%) = 258(1), 240(2), 195(4), 169(6),
117(100), 89(20), 71(25). HRMS (ESI-TOF) calcd for C15H30O3 [M
+ Na]+: 281.2087, Found: 281.2093.
Ethyl 3-hydroxy-4-phenylbutanoate (3f).9a 381.6 mg, 91% yield,
colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.30 – 7.22 (m, 2H), 7.21
– 7.13 (m, 3H), 4.26 – 4.15 (m, 1H), 4.10 (q, J = 7.1 Hz, 2H), 2.88 (d,
J = 3.8 Hz, 1H), 2.81 (dd, J = 13.6, 7.1 Hz, 1H), 2.70 (dd, J = 13.6, 6.2
Hz, 1H), 2.46 (dd, J = 16.4, 3.8 Hz, 1H), 2.37 (dd, J = 16.4, 8.5 Hz,
1H), 1.20 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ
Ethyl 4-(benzyloxy)-3-hydroxybutanoate (3l).17d 242.7 mg, 51% yield,
colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.39 – 7.27 (m, 5H), 4.56
(s, 2H), 4.29 – 4.20 (m, 1H), 4.15 (q, J = 7.1 Hz, 2H), 3.54 – 3.49 (m,
1H), 3.47 (dd, J = 9.2, 5.5 Hz, 1H), 3.06 (s, 1H), 2.54 (d, J = 6.3 Hz,
2H), 1.25 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ
172.2, 138.0, 128.5, 127.9, 127.8, 73.5, 73.2, 67.3, 60.8, 38.4, 14.2. GC-
MS (EI, 70 eV): m/z (%) = 238.1(1), 163(2), 132(10), 117(20),
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