The Journal of Organic Chemistry
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mmol) colorless liquid; bp 126 °C (lit. 125.99 °C);56 1H NMR (400
MHz, CDCl3) δ 4.07 (t, J = 6.7 Hz, 2H), 2.05 (s, 3H), 1.62−1.60 (m,
2H), 1.47−1.29 (m, 2H), 0.94 (t, J = 7.4 Hz, 3H); 13C{1H} NMR
OD-H retention time of the racemic compound (in min): tR = 15.32,
1
tR = 25.27.
2
(R)-1-Phenylpropane-1,3-diyl Diacetate ((R)-3o). Purification by
1
(100 MHz, CDCl3) δ 171.1, 64.3, 30.6, 20.9, 19.1, 13.6. The H and
column chromatography (hexanes/EtOAc, 10:1 v/v) afforded
13C{1H} NMR data were in accordance with those reported in the
literature.57 n-Butyl acetate, 3.58 min GC retention time; n-butanol,
2.89 min GC retention time.
n-Hexyl Acetate (3g). Purification by column chromatography
(hexanes/EtOAc, 10:1 v/v) afforded product 3g; 87% (125 mg. 0.87
mmol) colorless liquid; bp 169 °C (lit. 170.9 °C);58 1H NMR (400
MHz, CDCl3) δ 4.04 (t, J = 6.8 Hz, 2H), 2.02 (s, 3H), 1.65−1.53 (m,
2H), 1.40−1.22 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 171.1, 64.6, 31.4, 28.5, 25.5, 22.4, 20.9, 13.9.
The 1H and 13C{1H} NMR data were in accordance with those
reported in the literature.59
2-Methylpropyl Acetate (3h). Purification by column chromatog-
raphy (hexanes/EtOAc, 10:1 v/v) afforded product 3h; 87% (101 mg,
0.87 mmol) colorless liquid; bp 117.5 °C (lit. 117.0−118.0 °C);60 1H
NMR (400 MHz, CDCl3) δ 3.80 (d, J = 6.7 Hz, 2H), 2.00 (s, 3H),
1.88 (dt, J = 14.8, 7.4 Hz, 1H), 0.88 (d, J = 6.8 Hz, 6H); 13C{1H}
NMR (100 MHz, CDCl3) δ 171.2, 70.5, 27.5, 20.7, 18.9. The 1H and
13C{1H} NMR data were in accordance with those reported in the
literature.61
20
product (R)-3o; 11% (26 mg, 0.11 mmol) colorless oil; [α]D
=
+62.8 (c 1.00, CHCl3), 92% ee (lit. for (S) enantiomer [α]D20 = −55.1
(c 0.5, CHCl3) with 82% ee).68 1H NMR (400 MHz, CDCl3) δ 7.39−
7.29 (m, 5H), 5.86 (dd, J = 8.2, 5.7 Hz, 1H), 4.18−3.98 (m, 2H),
2.25−2.08 (m, 2H), 2.07 (s, 3H), 2.02 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 170.9, 170.0, 139.8, 128.5, 128.1, 126.3, 72.8, 60.6,
35.2, 21.1, 20.8. The 1H and 13C{1H} NMR data were in accordance
with those reported in the literature.68 HPLC AD retention time of
the racemic compound (in min): tR = 6.96, tR = 8.35.
1
2
(R)-2-Hydroxy-2-phenylethyl Acetate ((R)-3p). Purification by
column chromatography (hexanes/EtOAc, 8:2 v/v) afforded product
20
(R)-3p; 25% (45 mg, 0.25 mmol) colorless oil; [α]D = −18.3 (c
1.00, CHCl3), 64% ee (lit. for (R) enantiomer [α]D20 = −26.8 (c 1.10,
CHCl3) with >99% ee).69 1H NMR (400 MHz, CDCl3) δ 7.47−7.32
(m, 5H), 4.99 (dd, J = 8.3, 3.1 Hz, 1H), 4.25 (ddd, J = 20.0, 11.5, 5.7
Hz, 2H), 2.13 (s, 3H); 13C{1H} (100 MHz, CDCl3) δ 171.2, 139.8,
128.5, 128.2, 126.1, 72.3, 69.3, 20.8. The 1H and 13C{1H} NMR data
were in accordance with those reported in the literature.69 HPLC
OD-H retention time of the racemic compound (in min): tR = 16.07,
1
3-Methylbut-2-enyl Acetate (3i). Purification by column chroma-
t
= 19.44.
tography (hexanes/EtOAc, 10:1 v/v) afforded product 3i; 91% (117
R2
1
mg, 0,91 mmol) colorless oil; H NMR (400 MHz, CDCl3) δ 5.36−
General Procedure for DKR Reaction. To a Schlenck flask,
5.23 (m, 1H), 4.52 (d, J = 7.3 Hz, 2H), 1.99 (s, 3H), 1.71 (s, 3H),
1.66 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.9, 138.7,
118.5, 61.2, 25.5, 20.8, 17.8. The 1H and 13C{1H} NMR data were in
accordance with those reported in the literature.62
Novozym 435 (20 mg), sodium carbonate (1 equiv), and ruthenium
catalyst A (5 mol %) were added under an argon atmosphere. Next,
toluene (1 mL) and then t-BuOK (100 μL of 0.5 M solution in THF,
5 mol %) were added and the mixture was stirred for 5 min at 60 °C
in a heating incubator. After that time, rac-4 (1.0 mmol, 1.0 equiv) in
toluene (1 mL) was added and incubated at 60 °C for 5 min. Next,
benzylidene 1,1-diacetate (2a) (1.5 mmol, 1.5 equiv) was added and
the reaction misxture was stirred at 60 °C in a heating incubator, then
filtrated through a silica pad, and washed with ethyl acetate. The
products were isolated by flash chromatography (hexanes/ethyl
acetate).
9-Decen-1-yl Acetate (3j). Purification by column chromatography
(hexanes/EtOAc, 10:1 v/v) afforded product 3j; 93% (184 mg, 0,93
1
mmol) colorless oil; H NMR (400 MHz, CDCl3) δ 5.82 (ddt, J =
16.9, 10.2, 6.7 Hz, 1H), 5.09−4.82 (m, 2H), 4.07 (t, J = 6.8 Hz, 2H),
2.11−1.97 (m, 5H), 1.67−1.58 (m, 2H), 1.43−1.27 (m, 10H);
13C{1H} NMR (100 MHz, CDCl3) δ 171.1, 139.1, 114.1, 64.6, 33.7,
1
29.3, 29.1, 29.0, 28.8, 28.5, 25.8, 20.9. The H and 13C{1H} NMR
data were in accordance with those reported in the literature.63
Cinnamyl Acetate (3k). Purification by column chromatography
(hexanes/EtOAc, 10:1 v/v) afforded product 3k; 88% (143 mg, 0.88
(R)-1-Phenethyl Acetate ((R)-(5a)). Purification by column
chromatography (hexanes/EtOAc, 10:1 v/v) afforded product (R)-
20
5a; 94% (115 mg, 0.94 mmol) colorless liquid; [α]D = +108.6 (c
1.00, CHCl3), >99% ee (lit. for (R) enantiomer [α]D20 = +102 (c 1.00,
CHCl3) with >99% ee);70 1H NMR (400 MHz, CDCl3) δ 7.33 (ddd, J
= 8.7, 4.5, 2.2 Hz, 5H), 5.89 (q, J = 6.6 Hz, 1H), 2.07 (s, 3H), 1.54 (d,
J = 6.6 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.2, 141.7,
128.4, 127.8, 126.0, 72.2, 22.1, 21.3. The 1H and 13C{1H} NMR data
were in accordance with those reported in the literature.70 GC
1
mmol) colorless oil; H NMR (400 MHz, CDCl3) δ 7.44−7.24 (m,
5H), 6.68 (d, J = 15.9 Hz, 1H), 6.31 (dt, J = 15.8, 6.4 Hz, 1H), 4.76
(dd, J = 6.4, 1.2 Hz, 2H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 170.7, 136.2, 134.2, 128.6, 128.0, 126.6, 123.2, 65.0, 20.9.
The 1H and 13C{1H} NMR data were in accordance with those
reported in the literature.64
retention time of the racemic compound (in min): tR = 17.70, tR
=
(2Z)-Pent-2-en-1-yl Acetate (3l). Purification by column chroma-
tography (hexanes/EtOAc, 10:1 v/v) afforded product 3l; 83% (106
mg, 0.83 mmol) light yellow oil; 1H NMR (400 MHz, CDCl3) δ 5.60
(ddd, J = 13.5, 9.8, 7.4 Hz, 1H), 5.46 (dddd, J = 9.2, 8.4, 4.9, 3.4 Hz,
1H), 4.58 (dd, J = 6.9, 0.4 Hz, 2H), 2.12−2.04 (m, 2H), 2.01 (s, 3H),
0.95 (t, J = 7.5 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.8,
1
2
18.23.
(R)-1-Phenyl-1-propyl Acetate ((R)-(5b)). Purification by column
chromatography (hexanes/EtOAc, 10:1 v/v) afforded product (R)-
20
5b; 92% (125 mg, 0,92 mmol) colorless liquid; [α]D = +110.3 (c
1.00, CHCl3), >99% ee (lit. for (R) enantiomer [α]D20 = +105 (c 1.00,
CHCl3) with >99% ee);71 1H NMR (400 MHz, CDCl3) δ 7.43−7.19
(m, 5H), 5.67 (t, J = 6.9 Hz, 1H), 2.07 (s, 3H), 2.00−1.72 (m, 2H),
0.88 (t, J = 7.4 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.3,
140.5, 128.3, 128.3, 127.7, 126.5, 126.5, 126.5, 126.5, 29.2, 21.2, 9.8.
The 1H and 13C{1H} NMR data were in accordance with those
reported in the literature.71 GC retention time of the racemic
compound (in min): tR = 18.09, tR = 18.78.
1
136.8, 122.6, 60.2, 20.8, 20.7, 13.9. The H and 13C{1H} NMR data
were in accordance with those reported in the literature.65
3-Phenylprop-2-ynyl Acetate (3m). Purification by column
chromatography (hexanes/EtOAc, 10:1 v/v) afforded product 3m;
1
94% (164 mg, 0.94 mmol) light yellow oil; H NMR (400 MHz,
CDCl3) δ 7.51−7.38 (m, 2H), 7.38−7.26 (m, 3H), 4.90 (s, 2H), 2.12
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.2, 131.8, 128.7,
1
2
1
128.2, 122.1, 86.4, 82.9, 52.8, 20.7. The H and 13C{1H} NMR data
(R)-4-Phenyl-2-butyl Acetate ((R)-(5c)). Purification by column
chromatography (hexanes/EtOAc, 10:1 v/v) afforded product (R)-
5c; 97% (186 mg, 0.97 mmol) colorless liquid; [α]D20 = +14.1 (c 1.00,
were in accordance with those reported in the literature.66
rac-3-Acetoxy-1-phenyl-propan-1-ol (3n). Purification by column
20
chromatography (hexanes/EtOAc, 8:2 v/v) afforded product 3n; 68%
CHCl3), 96% ee (lit. for (R) enantiomer [α]D = +13 (c 1.00,
1
CHCl3) with 94% ee);71 1H NMR (400 MHz, CDCl3) δ 7.33−7.10
(m, 5H), 4.94 (ddd, J = 7.7, 6.3, 5.1 Hz, 1H), 2.74−2.53 (m, 2H),
2.03 (s, 3H), 1.86 (ddddd, J = 14.9, 13.9, 11.5, 6.3, 3.5 Hz, 2H), 1.25
(d, J = 6.3 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7,
(132 mg, 0.68 mmol) colorless oil; H NMR (400 MHz, CDCl3) δ
7.42−7.26 (m, 5H), 4.79 (dd, J = 8.1, 5.2 Hz, 1H), 4.31 (ddd, J =
11.2, 7.6, 5.8 Hz, 1H), 4.12 (dt, J = 11.4, 5.9 Hz, 1H), 2.11−1.99 (m,
5H); 13C{1H} NMR (100 MHz, CDCl3) δ 171.2, 143.9, 128.5, 128.5,
125.7, 125.7, 125.7, 71.3, 61.5, 37.9, 20.9. The 1H and 13C{1H} NMR
data were in accordance with those reported in the literature.67 HPLC
1
141.5, 128.4, 128.3, 125.9, 70.5, 37.5, 31.8, 21.2, 20.0. The H and
13C{1H} NMR data were in accordance with those reported in the
6338
J. Org. Chem. 2021, 86, 6331−6342