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stirred at room temperature for 8 h. Then 0.5 mL of acetic anhydride
was added, and the resulting mixture was stirred at room temperature
overnight. The reaction was quenched by adding 3.0 equiv of NaOAc.
After the solvent was removed under vacuum, the residue was purified
by flash chromatography to afford 2ia in 99% yield (colorless oil)
(syn/anti > 19:1): 1H NMR (400 MHz, CDCl3) δ 7.36−7.33 (m, 5H),
6.27 (d, J = 4.0 Hz, 1H), 5.33 (d, J = 4.0 Hz, 1H), 3.70 (s, 3H), 2.13
(s, 3H), 2.09 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 169.7, 169.3,
167.4, 135.4, 128.6, 128.4, 126.6, 74.0, 73.6, 52.4, 20.7, 20.2.
anti-3-Methoxy-3-oxo-1-(4-fluorophenylpropane)-1,2-diyl Diace-
tate (2lb). Employing the same procedure as 2ib, compound 2 lb was
isolated in 97% yield (colorless oil) (syn/anti = 1:3.4): 1H NMR (400
MHz, CDCl3) δ 7.37−7.33 (m, 2H), 7.07 (t, J = 8.4 Hz, 2H), 6.19 (d,
J = 5.2 Hz, 1H), 5.47 (d, J = 5.2 Hz, 1H), 3.71 (s, 3H), 2.12 (s, 3H),
2.11 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 169.5, 169.1, 167.0,
162.7 (d, J = 246.1 Hz), 130.92 (d, J = 3.2 Hz), 129.2 (d, J = 8.3 Hz),
115.2 (d, J = 21.6 Hz), 73.1, 72.5, 52.2, 20.6, 20.2; HRMS (ESI) calcd
for C14H15FO6Na [M + Na]+ 321.07449, found 321.07376.
General Procedure C (Diacetoxylation of Terminal Al-
kenes). To the solution of alkene (1.0 mmol) and PhI(OAc)2 (322
mg, 1.0 mmol) in AcOH (5.0 mL) and Ac2O (0.2 mL) was added
BF3·OEt2 (13 μL, 0.1 mmol). The resulting mixture was stirred at
corresponding temperature for the desired time and then quenched by
adding 0.2 equiv of NaOAc. After the solvent was removed under
vacuum, the residue was purified by flash chromatography to afford the
product.
anti-3-Methoxy-3-oxo-1-phenylpropane-1,2-diyl Diacetate
(2ib). To the solution of PhI(OAc)2 (1.0 mmol) in AcOH (1.0
mL) and Ac2O (0.1 mL) was added BF3·OEt2 (3.0 mmol), and the
mixture was stirred at room temperature under Ar atmosphere for 30
min before trans-methyl cinanmate (1.0 mmol) was added. The
resulting mixture was stirred at room temperature for 4 h, and the
second batch of PhI(OAc)2 (0.5 mmol) was added. The reaction
mixture was further stirred for 2.5 h and then quenched by adding 3.0
equiv of NaOAc. After the solvent was removed under vacuum, the
residue was purified by flash chromatography to afford 2ib in 94%
1-Phenylethane-1,2-diyl Diacetate (4a).3k General procedure C, 2
h at room temperature, 4a was isolated in 98% yield (colorless oil): 1H
NMR (400 MHz, CDCl3) δ 7.37−7.32 (m, 5H), 6.02 (dd, J = 4.0, 8.0
Hz, 1H), 4.34 (dd, J = 4.0, 12.0 Hz, 1H), 4.28 (dd, J = 8.0, 12.0 Hz,
1H), 2.11 (s, 3H), 2.05 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
170.5, 169.9, 136.4, 128.5, 128.5, 126.6, 73.2, 66.0, 21.0, 20.6.
1-p-Tolylethane-1,2-diyl Diacetate (4b).22 General procedure C, 2
h at room temperature, 4b was isolated in 84% yield (colorless oil): 1H
NMR (400 MHz, CDCl3) δ 7.26 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 8.0
Hz, 2H), 5.98 (dd, J = 4.4, 7.2 Hz, 1H), 4.34−4.25 (m, 2H), 2.34 (s,
3H), 2.10 (s, 3H), 2.05 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
170.5, 170.0, 138.4, 133.5, 129.3, 126.6, 73.2, 66.0, 21.1, 21.0, 20.7.
1-(4-Fluorophenyl)ethane-1,2-diyl Diacetate (4c).3k General pro-
cedure C, 2 h at room temperature, 4c was isolated in 91% yield
1
yield (colorless oil) (syn/ = 1:9.1): H NMR (400 MHz, CDCl3) δ
7.35 (br, 5H), 6.21 (d, J = 5.2 Hz, 1H), 5.48 (d, J = 5.2 Hz, 1H), 3.71
(s, 3H), 2.12−2.11 (br, 6H); 13C NMR (100 MHz, CDCl3) δ 169.5,
169.2, 167.1, 135.0, 128.6, 128.2, 127.2, 73.3, 73.2, 52.2, 20.6, 20.2;
HRMS (ESI) calcd for C14H16O6Na [M + Na]+ 303.08391, found
303.08388.
syn-3-Methoxy-3-oxo-1-(4-Chlorophenylpropane)-1,2-diyl Diace-
tate (2ja). Employing the same procedure as 2ia, 16 h at room
temperature, compound 2ja was isolated in 98% yield (colorless oil)
(syn/anti > 19:1): 1H NMR (400 MHz, CDCl3) δ 7.35−7.29 (m, 4H),
6.23 (d, J = 4.0 Hz, 1H), 5.30 (d, J = 4.0 Hz, 1H), 3.72 (s, 3H), 2.12
(s, 3H), 2.10 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 169.7, 169.3,
167.3, 134.7, 134.1, 128.7, 128.2, 73.8, 73.1, 52.7, 20.7, 20.3; HRMS
(ESI) calcd for C14H15ClO6Na [M + Na]+ 337.04494, found
337.04442.
1
(colorless oil): H NMR (400 MHz, CDCl3) δ 7.35 (dd, J = 5.6, 8.4
Hz, 2H), 7.05 (t, J = 8.4 Hz, 2H), 5.99 (dd, J = 4.0, 7.2 Hz, 1H), 4.33−
4.24 (m, 2H), 2.11 (s, 3H), 2.05 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 170.3, 169.7, 162.6 (d, J = 245.8 Hz), 132.3 (d, J = 3.2 Hz),
128.4 (d, J = 8.3 Hz), 115.4 (d, J = 21.5 Hz), 72.5, 65.7, 20.8, 20.5.
1-[4-(tert-Butyl)phenyl]ethane-1,2-diyl Diacetate (4d). General
procedure C, 2 h at room temperature, 4d was isolated in 90% yield
anti-3-Methoxy-3-oxo-1-(4-Chlorophenylpropane)-1,2-diyl Diac-
etate (2jb). Employing the same procedure as 2ib, 2jb was isolated in
1
93% yield (colorless oil) (syn/anti = 1:6.3): H NMR (400 MHz,
CDCl3) δ 7.35−7.26 (m, 4H), 6.18 (d, J = 5.2 Hz, 1H), 5.47 (d, J = 5.2
Hz, 1H), 3.72 (s, 3H), 2.12 (s, 3H), 2.11 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 169.4, 169.0, 166.9, 134.5, 133.6, 128.6, 128.4, 73.0,
72.5, 52.3, 20.5, 20.2; HRMS (ESI) calcd for C14H15ClO6Na [M +
Na]+ 337.04494, found 337.04477.
syn-3-Methoxy-3-oxo-1-(4-bromophenylpropane)-1,2-diyl Diace-
tate (2ka). Employing the same procedure as 2ia, 20 h at room
temperature, compound 2ka was isolated in 100% yield (colorless oil)
(syn/anti > 19:1): 1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 8.4 Hz,
2H), 7.24 (d, J = 8.4 Hz, 2H), 6.22 (d, J = 4.0 Hz, 1H), 5.30 (d, J = 4.0
Hz, 1H), 3.72 (s, 3H), 2.12 (s, 3H), 2.10 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 169.7, 169.3, 167.2, 134.6, 131.6, 128.4, 122.8, 73.7,
73.1, 52.6, 20.7, 20.3; HRMS (ESI) calcd for C14H15BrO6Na [M +
Na]+ 380.99442, found 380.99447.
1
(colorless oil): H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz,
2H), 7.29 (d, J = 8.4 Hz, 2H), 6.01 (dd, J = 4.0, 8.0 Hz, 1H), 4.33 (dd,
J = 4.0, 12.0 Hz, 1H), 4.28 (dd, J = 8.0, 12.0 Hz, 1H), 2.10 (s, 3H),
2.06 (s, 3H), 1.31 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 170.4,
169.9, 151.5, 133.4, 126.4, 125.4, 73.0, 66.0, 34.5, 31.2, 21.0, 20.6;
HRMS (ESI) calcd for C16H22O4Na [M + Na]+ 301.14103, found
301.14073.
Acetic Acid 2-Acetoxy-3-benzyloxypropyl Ester (4e).3k General
procedure C, 20 h at 50 °C, 4e was isolated in 74% yield (colorless
1
oil): H NMR (400 MHz, CDCl3) δ 7.36−7.27 (m, 5H), 5.24−5.19
(m, 1H), 4.56 (d, J = 12.0 Hz, 1H), 4.51 (d, J = 12.0 Hz, 1H), 4.34
(dd, J = 4.0, 12.0 Hz, 1H), 4.19 (dd, J = 6.4, 12.0 Hz, 1H), 3.59 (d, J =
5.2 Hz, 1H), 2.07 (s, 3H), 2.03 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 170.5, 170.2, 137.6, 128.3, 127.7, 127.6, 73.2, 70.2, 68.0, 62.7, 20.9,
20.6.
anti-3-Methoxy-3-oxo-1-(4-bromophenylpropane)-1,2-diyl Diac-
etate (2kb). Employing the same procedure as 2ib, compound 2kb
was isolated in 87% yield (colorless oil) (syn/anti = 1:7.1): H NMR
Acetic Acid 2-Acetoxydecyl Ester (4f).3k General procedure C, the
reaction was performed at room temperature for 8 h by using 0.4 equiv
of BF3·OEt2, and 4f was isolated in 94% yield (colorless oil): 1H NMR
(400 MHz, CDCl3) δ 5.10−5.04 (m, 1H), 4.23 (dd, J = 3.2, 12.0 Hz,
1H), 4.03 (dd, J = 6.4, 12.0 Hz, 1H), 2.06 (s, 3H), 2.05 (s, 3H), 1.57−
1.56 (br, 2H), 1.30−1.28 (m, 8H), 0.89 (t, J = 5.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 170.6, 170.4, 71.5, 65.0, 31.5, 30.6, 28.9, 25.0,
22.4, 20.9, 20.6, 13.9.
1
(400 MHz, CDCl3) δ 7.49 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz,
2H), 6.16 (d, J = 4.8 Hz, 1H), 5.46 (d, J = 4.8 Hz, 1H), 3.72 (s, 3H),
2.12 (s, 3H), 2.11 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 169.4,
169.0, 166.9, 134.1, 131.4, 128.9, 122.8, 73.0, 72.6, 52.3, 20.6, 20.3;
HRMS (ESI) calcd for C14H15BrO6Na [M + Na]+ 380.99442, found
380.99429.
syn-3-Methoxy-3-oxo-1-(4-fluorophenylpropane)-1,2-diyl Diace-
tate (2la). Employing the same procedure as 2ia, 12 h at room
temperature, compound 2la was isolated in 99% yield (colorless oil)
(syn/anti = 11:1): 1H NMR (400 MHz, CDCl3) δ 7.37−7.34 (m, 2H),
7.05 (t, J = 8.4 Hz, 2H), 6.24 (d, J = 4.0 Hz, 1H), 5.30 (d, J = 4.0 Hz,
1H), 3.70 (s, 3H), 2.12 (s, 3H), 2.10 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 169.6, 169.2, 167.2, 162.6 (d, J = 246.1 Hz), 131.3 (d, J =
3.3 Hz), 128.6 (d, J = 8.3 Hz), 115.3 (d, J = 21.6 Hz), 73.8, 73.0, 52.4,
20.6, 20.1; HRMS (ESI) calcd for C14H15FO6Na [M + Na]+
321.07449, found 321.07432.
4-(4-Methoxyphenyl)butane-1,2,4-triyl Triacetate (4g). General
procedure C, 24 h at room temperature, 4g was isolated in 78% yield
(colorless oil) (dr = 1.7:1): 1H NMR (400 MHz, CDCl3) δ 7.29−7.23
(m, 2H), 6.87 (d, J = 8.4 Hz, 2H), 5.80−5.75 (m, 1H), 5.26−5.20 (m,
0.6H), 4.97−4.92 (m, 0.4H), 4.26 (td, J = 3.6, 12.0 Hz, 1H), 4.03 (dd,
J = 5.6, 12.0 Hz, 1H), 3.79 (s, 3H), 2.34−2.07 (m, 2H), 2.05−2.03 (m,
9H); 13C NMR (100 MHz, CDCl3) δ 170.5, 170.3, 170.0, 169.9,
159.5, 159.4, 131.9, 131.3, 127.9, 127.8, 114.0, 113.9, 72.4, 71.1, 68.6,
67.8, 65.0, 64.6, 55.2, 55.1, 37.1, 37.0, 21.1, 21.0, 20.8, 20.7, 20.6;
10002
dx.doi.org/10.1021/jo201752y | J. Org. Chem. 2011, 76, 9997−10004