7
1
3
(
m, 6H), 0.88 (t, J = 8.0 Hz, 3H) ppm; C NMR (100 MHz,
Pale yellow crystalline solid, m.p. 36-38 °C (petroleum ether),
ACCEPTED MANUSCRIPT
CDCl ) δ 209.2, 169.6, 163.3, 143.3, 52.3, 36.6, 34.3, 31.8,
9.7, 28.0, 23.2, 22.5, 14.0 ppm; FT-IR νmax 1171 (s), 1194 (s),
(lit. 37-38 °C), (1 mmol scale, 156 mg, 74%), R (9:1,
hexane:EtOAc) 0.2. H NMR (400 MHz, CDCl ) δ 7.86 (d, J =
7.7 Hz, 1H), 7.72 – 7.66 (m, 1H), 7.49 – 7.43 (m, 2H), 4.68 (dd, J
= 7.5, 3.2 Hz, 1H), 3.86 (dd, J = 18.4, 7.7 Hz, 1H), 3.45 (dd, J =
18.1, 3.0 Hz, 1H) ppm; C NMR (100 MHz, CDCl ) δ 199.6,
3
C
f
1
2
1
(
3
435 (m), 1644 (m), 1698 (s), 1738 (s), 2860 (w), 2929 (w), 2954
-
1
+
+
w) cm ; GC-MS R 4.70 min, m/z 224 [M] , 193 [M-OMe] , 154
t
+ +
13
[
M-C H ] , 151 [M-CH CO Me] .
5
11
2
2
3
C
1
51.1, 136.0, 133.6, 128.3, 126.4, 125.1, 44.1, 38.0 ppm; FT-IR
-1
3
7
3
-Methyl-2-pentylcyclopent-2-enone (2b)
νmax 1208 (s), 1275 (s), 1460 (w), 1604 (m), 1717 (s) cm ; GC-
MS R 4.35 min, m/z 212 [M] , 210 [M] , 132 [M-Br] .
t
+ + +
Colourless liquid (1 mmol scale, 75% isomerically pure starting
material, 112 mg, 90%), R (9:1, hexane:EtOAc) 0.2. H NMR
400 MHz, CDCl ) δ 2.50 (m, 2H), 2.37 (m, 2H), 2.17 (t, J = 7.6
1
f
42
(
2-Bromo-2-methyl-2,3-dihydro-1H-inden-1-one (9b)
3
Hz, 2H), 2.06 (s, 3H), 1.43 – 1.21 (m, 6H), 0.88 (t, J = 7.2 Hz,
White crystalline solid, m.p. 70-71 °C (petroleum ether), (lit.71-
13
3
3
1
H) ppm; C NMR (100 MHz, CDCl ) δC 209.7, 170.0, 140.8,
72 °C), (1 mmol scale, 153 mg, 68%), R (9:1, hexane:EtOAc)
3
f
1
4.3, 31.8, 31.5, 28.1, 23.0, 22.5, 17.2, 14.0 ppm; FT-IR ν
385 (w), 1645 (m), 1695 (s), 2858 (w), 2926 (w), 1956 (w) cm ;
0.3. H NMR (400 MHz, CDCl ) δ 7.90 (d, J = 7.6 Hz, 1H), 7.69
max
3
-
1
(td, J = 7.5, 1.2 Hz, 1H), 7.50 – 7.43 (m, 2H), 3.82 (d, J = 18.2
+
+
13
GC-MS R 3.89 min, m/z 166 [M] , 151 [M-Me] .
Hz, 1H), 3.51 (d, J = 18.2 Hz, 1H), 1.99 (s, 3H) ppm; C NMR
t
(
100 MHz, CDCl ) δ 200.3, 149.1, 135.8, 132.7, 128.3, 126.3,
3 C
3
7
2
-Pentylcyclopent-2-enone (3b)
125.7, 59.5, 46.4, 26.8 ppm; FT-IR νmax 1045 (m), 1212 (m),
-1
Pale yellow liquid (1 mmol scale, 90% isomerically pure starting
material, 122 mg, 89%), R (9:1, hexane:EtOAc) 0.2. H NMR
1286 (m), 1465 (m), 1605 (m), 1715 (s) cm ; GC-MS R 4.27
t
+ + +
1
min, m/z 226 [M] , 224 [M] , 145 [M-Br] .
f
(
400 MHz, CDCl ) δ 7.31 (m, 1H), 2.60 – 2.54 (m, 2H), 2.43 –
3
2
4
.38 (m, 2H), 2.17 (m, 2H), 1.54 – 1.44 (m, 2H), 1.38 – 1.24 (m,
13
3-Bromo-6-methylhept-5-en-2-one (11b)
H), 0.90 (t, J = 6.8 Hz, 3H) ppm; C NMR (100 MHz, CDCl )
Brown liquid (1.25 mmol scale, 117 mg, 46%), R (9:1,
3
f
1
δ 210.1, 157.2, 146.6, 34.6, 31.6, 27.4, 26.4, 24.7, 22.4, 14.0
hexane:EtOAc) 0.3. H NMR (400 MHz, CDCl ) δ 4.22 (dd, J =
C
3
-
1
ppm; FT-IR νmax 1696 (s), 2860 (w), 2926 (w), 2956 (w) cm ;
GC-MS R 3.63 min, m/z 152 [M] , 137 [M-Me] , 123 [M-Et] .
11.3, 1.5 Hz, 1H), 2.92 – 2.65 (m, 2H), 2.21 (s, 3H), 2.09 – 2.01
(m, 1H), 2.00 (s, 3H), 1.86 (s, 3H) ppm; C NMR (100 MHz,
+
+
+
13
t
CDCl ) δ 207.3, 67.9, 66.1, 42.3, 35.0, 30.1, 29.9, 28.8 ppm;
3
C
3
8
-1
2
-Benzylcyclopent-2-enone (4b)
FT-IR νmax 1097 (s), 1370 (m), 1715 (s), 2977 (w) cm ; GC-MS
+
+
+
Colourless liquid (1 mmol scale, 67% isomerically pure starting
material, 22 mg, 20%), R (8:2, hexane:EtOAc) 0.2. H NMR
R 4.07 min, m/z 207 [M+H] , 205 [M+H] , 125 [M-Br] ; ASAP-
t
1
+
HRMS m/z found [M+H] 205.0221, C H BrO requires
f
8
14
(
2
400 MHz, CDCl ) δ 7.35 – 7.20 (m, 5H), 7.17 (m, 1H), 3.51 (m,
H), 2.56 (m, 2H), 2.50 – 2.42 (m, 2H) ppm; C NMR (100
205.0228 (ꢀ = 3.4 ppm).
3
13
43
MHz, CDCl ) δ 209.2, 158.8, 146.1, 138.9, 128.9, 128.5, 126.3,
1-Bromocyclohexanecarbaldehyde (12b)
3
C
3
1
4.6, 31.4, 26.5 ppm; FT-IR ν
703 (m), 790 (w), 1001 (w),
Brown liquid (1 mmol scale, 165 mg, 86%), R (9:1,
max
f
-
1
1
453 (w), 1496 (w), 1695 (s) cm ; GC-MS R 4.37 min, m/z 172
hexane:EtOAc) 0.5. H NMR (400 MHz, CDCl ) δ 9.37 (s, 1H),
t
3
+
13
[
M] .
2.16 – 1.96 (m, 4H), 1.88 – 1.20 (m, 6H) ppm. C NMR (100
MHz, CDCl ) δ 192.8, 71.6, 34.4, 25.0, 23.2 ppm; FT-IR ν
3
C
max
3
9
-1
2
-Ethylcyclopent-2-enone (5b)
1723 (s), 2858 (w), 2936 (m) cm ; GC-MS R 3.15 min, m/z 192
t
+ + +
Yellow liquid (1 mmol scale, 50% isomerically pure starting
material, 31 mg, 62%), R (9:1, hexane:EtOAc) 0.3. H NMR
400 MHz, CDCl ) δ 7.32 (m, 1H), 2.61 – 2.55 (m, 2H), 2.45 –
[M] , 190 [M] , 111 [M-Br] .
1
f
44
(
2-Hydroxy-2-phenylpropanal (13b)
3
2
.40 (m, 2H), 2.26 – 2.17 (m, 2H), 1.12 (t, J = 7.5 Hz, 3H) ppm;
C NMR (100 MHz, CDCl ) δ 210.0, 156.6, 147.9, 34.7, 26.4,
α-Bromo compound (2-bromo-2-phenylpropanal) underwent
13
hydrolysis during purification. Pale yellow oil (1.1 mmol scale,
3
C
-
1
1
1
8.1, 12.1 ppm; FT-IR νmax 1262 (w), 1715 (s), 2926 (m) cm ;
85 mg, 57%). H NMR (400 MHz, CDCl ) δ 9.58 (s, 1H), 7.52 –
3
+
+
13
GC-MS R 2.67 min, m/z 110 [M] , 95 [M-Me] .
7.33 (m, 5H), 3.92 (br s, 1H), 1.73 (s, 3H) ppm; C NMR (100
t
MHz, CDCl ) δ 199.9, 139.2, 128.9, 128.2, 125.8, 79.1, 23.6
3
C
5
-Bromo-2-methylcyclopent-2-enone (6b)
ppm; FT-IR ν 697 (s), 1070 (m), 1729 (m), 2982 (m), 3451 (w,
max
-1 + +
Colourless liquid (1.4 mmol scale, 85% isomerically pure starting
material, 35 mg, 17%), R (9:1, hexane:EtOAc) 0.2. H NMR
br) cm ; GC-MS R 3.34 min, m/z 133 [M-OH] , 121 [M-CHO] .
t
1
f
45
(400 MHz, CDCl ) δ 7.33 (m, 1H), 5.11 (m, 1H), 3.07 (dd, J =
2-Pentylphenol (14b)
3
1
9.6, 6.2 Hz, 1H), 2.79 (dd, J = 19.6, 1.6 Hz, 1H), 1.88 (t, J = 1.6
Colourless liquid (0.6 mmol scale, 42 mg, 42%), R (9:1,
f
13
1
Hz, 3H) ppm; C NMR (100 MHz, CDCl ) δC 204.7, 156.2,
hexane:EtOAc) 0.2. H NMR (400 MHz, CDCl ) δ 7.16 – 7.07
3
3
1
43.8, 45.2, 42.1, 10.0 ppm; FT-IR ν 918 (m), 1069 (w), 1187
(m, 2H), 6.89 (td, J = 7.4, 1.2 Hz, 1H), 6.79 (dd, J = 8.0, 1.2 Hz,
max
-
1
+
+
(w), 1709 (s) cm ; GC-MS R 3.13 min, m/z 176 [M] , 174 [M] ,
1H), 4.81 (s, 1H), 2.63 (m, 2H), 1.71 – 1.59 (m, 2H), 1.43 – 1.33
t
+
+
13
9
5 [M-Br] ; ASAP-HRMS m/z found [M+H] 176.9738,
(m, 4H), 0.96 – 0.89 (m, 3H); C NMR (100 MHz, CDCl ) δC
3
C H BrO requires 176.9738 (ꢀ = 0 ppm).
153.4, 130.2, 128.6, 127.0, 120.8, 115.2, 31.7, 29.9, 29.5, 22.6,
6
8
1
4.1; FT-IR νmax 751 (s), 1218 (s), 1230 (s), 1367 (s), 1455 (s),
4
0
-1
2
-Bromocyclopentanone (7b)
1740 (s), 2929 (m), 3430 (w, br) cm ; GC-MS R 3.96 min, m/z
t
+ + +
Colourless liquid (1 mmol scale, 51 mg, 31%), Rf (8:2,
hexane:EtOAc) 0.4. H NMR (400 MHz, CDCl ) δ 4.28 – 4.22
164 [M] , 107 [M-C H ] , 77 [C H ] .
4 9 6 5
1
3
(
m, 1H), 2.48 – 2.34 (m, 2H), 2.31 – 2.16 (m, 3H), 2.09 – 1.98
4.3 Procedure for Catalytic Oxidation of 16a
13
(m, 1H) ppm; C NMR (100 MHz, CDCl ) δ 211.2, 48.1, 35.0,
3
C
-
1
3
3.9, 20.2 ppm; FT-IR νmax 1149 (s), 1741 (s), 2972 (w) cm ;
1,2-Bis(4-methoxyphenyl)propan-1-one (16a), (163 mg, 0.60
mmol) was dissolved in MeCN (5 mL) in a microwave vial, the
+
+
+
GC-MS R 2.88 min, m/z 164 [M] , 162 [M] , 83 [M-Br] .
t
solution was degassed and then saturated with O . Copper(II)
bromide (27 mg, 0.12 mmol, 20 mol%) was then added and the
vial was sealed. The solution was stirred at 85 °C under
2
41
2
-Bromo-1-indanone (8b)