6
Tetrahedron
4.2.9(R)-1-(3,4-dimethoxyphenyl)-3,4-dihydroxybutan-1-
0.18, CHCl3); HRMS (ESI) calcd for C10H11BrNaO3 [M +H]+
ACCEPTED MANUSCRIPT
one (11e).
280.9784, found 280.9783.
1
Yield: 80%; H NMR (400 MHz, MeOD) δ 7.71 (dd, J = 8.4,
2.0 Hz, 1H), 7.58 (d, J = 2.0 Hz, 1H), 7.06 (d, J = 8.5 Hz, 1H),
4.27 (p, J = 5.8 Hz, 1H), 3.92 (d, J = 11.3 Hz, 6H), 3.61 (d, J =
5.4 Hz, 2H), 3.16 (d, J = 6.2 Hz, 2H); 13C NMR (101 MHz,
MeOD) δ 199.6, 155.1, 150.4, 131.7, 124.5, 111.7, 111.7, 70.1,
The enantiomeric excess was determined by chiral HPLC after
conversion to the corresponding TBS ether.
4.2.14 (R)-1-(4-bromophenyl)-4-((tert-butyldimethylsilyl)
oxy)-3-hydroxybutan-1-one (11g-OTBS).
25
66.9, 56.5, 56.4, 42.9; [α]D = + 29.2 (c 1.0, CHCl3). HRMS
1
(ESI) calcd for C12H16O5 [M+H]+ 241.1071, found 241.1081.
Yield: 84%; H NMR (400 MHz, MeOD) δ 7.99 – 7.89 (m,
2H), 7.75 – 7.63 (m, 2H), 4.26 (dq,
J
= 7.5, 5.3 Hz, 1H),
= 23.9,
J = 2.8 Hz, 9H), 0.11 (d, J = 3.2
The enantiomeric excess was determined by chiral HPLC
after conversion to the corresponding TBS ether.
3.70 (ddd, = 34.8, 10.2, 5.5 Hz, 2H), 3.18 (ddd,
J
J
16.3, 6.2 Hz, 2H), 0.93 (d,
Hz, 6H); 13C NMR (100 MHz, MeOD) δ 199.7, 137.5,
4.2.10(R)-4-((tert-butyldimethylsilyl)oxy)-1-(3,4-
dimethoxyphenyl)-3-hydroxybutan-1-one (11e-OTBS).
25
133.0, 131.1, 129.1, 69.9, 68.0, 43.4, 26.4, 19.2, -5.3; [α]
D
= + 19.1 (c 0.36, CHCl3); HRMS (ESI) calcd for
C16H26BrO3Si [M+H]+ 373.0829, found 373.0822; ee of 11g-
OTBS : 87%, determined by HPLC analysis, Daicel,
Chiralpak AD-H column (25 cm × 4.6 mm × 5 µm), n-
hexane/isopropanol = 97/3, 1 mL/min, 254 nm, 30°C, tR
(major) = 10.399 min, tR (minor) = 13.955 min.
1H NMR (400 MHz, MeOD) δ 7.71 (dd,
1H), 7.58 (d, = 2.0 Hz, 1H), 7.06 (d, = 8.5 Hz, 1H), 4.27
(dq, = 7.5, 5.3 Hz, 1H), 3.93 (d, = 12.6 Hz, 6H), 3.71
(ddd, = 31.1, 10.2, 5.5 Hz, 2H), 3.17 (ddd, = 23.7, 16.1,
6.2 Hz, 2H), 0.94 (s, 9H), 0.12 (d,
= 3.0 Hz, 6H); 13C NMR
J = 8.4, 2.0 Hz,
J
J
J
J
J
J
J
(100 MHz, MeOD) δ 199.6, 155.2, 150.4, 131.7, 124.5,
4.2.15 (R)-1-(3-bromophenyl)-3, 4-dihydroxybutan-1-one
11h).
Yield: 87%;1H NMR (400 MHz, Acetone) δ 8.03 (d, J = 1.6 Hz,
111.8, 111.7, 70.2, 68.1, 56.5, 56.4, 42.9, 26.4, 19.2, -5.2;
(
25
[α
]
= + 17.5 (c 0.4, CHCl3); HRMS (ESI) calcd for
D
C18H31O5Si [M +H]+ 355.1935, found 355.1935; ee of 11e-
OTBS : 90%, determined by HPLC analysis, Daicel,
Chiralpak AD-H column (25 cm × 4.6 mm × 5 µm), n-
hexane/isopropanol = 97/3, 1 mL/min, 254 nm, 30°C, tR
(major) = 18.221 min, tR (minor) = 21.239 min.
1H), 7.91 (d, J = 7.8 Hz, 1H), 7.69 (dd, J = 7.9, 0.9 Hz, 1H), 7.39
(t, J = 7.9 Hz, 1H), 4.23 – 4.08 (m, 1H), 3.81 (s, 1H), 3.48 (d, J =
5.4 Hz, 2H), 3.09 (d, J = 6.0 Hz, 2H); 13C NMR (100 MHz,
Acetone) δ 197.8, 139.6, 135.6, 130.9, 130.7, 127.1, 122.3, 68.8,
25
65.9, 42.5; [α]D = + 28.2 (c 0.36, CHCl3); HRMS (ESI) calcd
4.2.11 (R)-1-(4-(benzyloxy)phenyl)-3,4-dihydroxybutan-1-
one (11f).
for C10H12BrO3 [M +H]+ 258.9964, found 258.9979
The enantiomeric excess was determined by chiral HPLC after
conversion to the corresponding TBS ether.
1
Yield: 84%; H NMR (400 MHz, Acetone) δ 8.05 – 7.94 (m,
2H), 7.50 (d, J = 7.2 Hz, 2H), 7.45 – 7.31 (m, 3H), 7.13 (dd, J =
9.3, 2.3 Hz, 2H), 5.24 (s, 2H), 4.29 – 4.14 (m, 1H), 3.79 (d, J =
43.3 Hz, 2H), 3.62 – 3.50 (m, 2H), 3.12 (dd, J = 6.1, 3.8 Hz, 2H);
4.2.16 (R)-1-(3-bromophenyl)-4-((tert-butyldimethylsilyl)
13C NMR (100 MHz, Acetone) δ 198.4, 163.6, 137.8, 131.7,
oxy)-3-hydroxybutan-1-one (11h-OTBS).
25
1H NMR (400 MHz, MeOD) δ 8.13 (t, J = 1.7 Hz, 1H), 7.99 (d,
J = 7.8 Hz, 1H), 7.85 – 7.75 (m, 1H), 7.46 (t, J = 7.9 Hz, 1H),
4.25 (dq, J = 7.5, 5.2 Hz, 1H), 3.70 (ddd, J = 38.0, 10.2, 5.5 Hz,
2H), 3.19 (ddd, J = 23.8, 16.2, 6.2 Hz, 2H), 0.93 (s, 9H), 0.10 (d,
J = 3.2 Hz, 6H); 13C NMR (100 MHz, MeOD) δ 199.3, 140.6,
137.0, 132.1, 131.6, 128.1, 123.8, 70.0, 68.0, 43.6, 26.4, 19.2, -
131.3, 129.4, 128.9, 128.5, 115.4, 70.7, 69.8, 66.8, 42.7; [α]D
=
+ 26.5 (c 0.2, CHCl3); HRMS (ESI) calcd for C17H19O4 [M +H]+
287.1278, found 287.1274.
The enantiomeric excess was determined by chiral HPLC after
conversion to the corresponding TBS ether.
25
4.2.12 (R)-1-(4-(benzyloxy)phenyl)-4-((tert-butyldimethyl
silyl)oxy)-3-hydroxybutan-1-one (11f-OTBS).
1H NMR (400 MHz, Acetone) δ 8.02 – 7.91 (m, 2H), 7.46
5.3; [α]D = + 16.8 (c 0.26, CHCl3); HRMS (ESI) calcd for
C16H26BrO3Si [M+H]+ 373.0829, found 373.0814; ee of 11h-
OTBS : 86%, determined by HPLC analysis, Daicel, Chiralpak
AD-H column (25 cm × 4.6 mm × 5 µm), n-hexane/isopropanol
= 97/3, 1 mL/min, 254 nm, 30°C, tR (major) = 9.382 min, tR
(minor) = 10.391 min.
(d,
J
= 7.2 Hz, 2H), 7.42 – 7.26 (m, 3H), 7.08 (d,
= 10.4, 5.3 Hz, 1H), 3.64 (qd,
= 10.1, 5.5 Hz, 2H), 3.08 (qd, = 16.1, 6.1 Hz, 2H), 0.87
= 3.6 Hz, 6H); 13C NMR (101 MHz,
J = 8.9 Hz,
2H), 5.20 (s, 2H), 4.18 (dq,
J
J
J
4.2.17 (R)-1-(4-chlorophenyl)-3,4-dihydroxybutan-1-one (11i).
(s, 9H), 0.05 (d,
J
1
Acetone) δ 198.3, 163.7, 137.9, 131.8, 131.4, 129.5, 129.0,
128.6, 115.5, 70.8, 68.0, 42.8, 26.4, 19.0, -5.1. [
Yield: 93%; H NMR (400 MHz, Acetone) δ 8.07 – 7.97 (m,
25
α
]
= +
2H), 7.60 – 7.51 (m, 2H), 4.31 – 4.17 (m, 1H), 3.84 (d, J = 45.6
Hz, 2H), 3.57 (d, J = 5.2 Hz, 2H), 3.24 – 3.11 (m, 2H); 13C NMR
(100 MHz, Acetone) δ 198.9, 139.5, 137.2, 130.9, 129.7, 69.8,
D
14.2 (c 0.2, CHCl3); HRMS (ESI) calcd for C23H33O4Si
[M+H]+ 401.2147, found 401.2143; ee of 11f-OTBS : 90%,
determined by HPLC analysis, Daicel, Chiralpak OD-H
column (25 cm × 4.6 mm × 5 µm), n-hexane/isopropanol =
97/3, 1 mL/min, 254 nm, 30°C, tR (major) = 16.785 min, tR
(minor) = 22.006 min.
25
66.9, 43.3; [α]D = + 29.2 (c 0.36, CHCl3); HRMS (ESI) calcd
for C10H11ClNaO3 [M +H]+ 237.0289, found 237.0288.
The enantiomeric excess was determined by chiral HPLC after
conversion to the corresponding TBS ether.
4.2.13 (R)-1-(4-bromophenyl)-3,4-dihydroxybutan-1-one
4.2.18 (R)-4-((tert-butyldimethylsilyl)oxy)-1-(4-chlorophen
(
11g).
1H NMR (400 MHz, MeOD) δ 7.95 (d, J = 8.5 Hz, 2H), 7.78 –
yl)-3-hydroxybutan-1-one (11i-OTBS).
1H NMR (400 MHz, MeOD) δ 8.01 (d,
7.53 (d, = 8.6 Hz, 2H), 4.26 (dq, = 10.6, 5.3 Hz, 1H),
3.70 (ddd, = 34.7, 10.2, 5.5 Hz, 2H), 3.19 (ddd, = 23.9,
J = 8.6 Hz, 2H),
7.65 (m, 2H), 4.27 (dq, J = 11.1, 5.5 Hz, 1H), 3.61 (d, J = 5.4 Hz,
2H), 3.25 – 3.14 (m, 2H); 13C NMR (101 MHz, MeOD) δ 199.8,
J
J
25
137.5, 133.0, 131.1, 129.1, 69.8, 66.8, 43.3; [α]D = + 39.3 (c
J
J