The Journal of Organic Chemistry
Page 6 of 8
1
3
1
1
28.5 (1C), 78.6 (1C), 26.7 (1C) IR: 3343, 3059, 2923, 1671,
3
2H), 1.88-1.74 (m, 1H). C{ H} NMR (101 MHz, CDCl ):
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1441, 1431, 1360, 1277, 1190, 797, 692. HRMS (ESI) m/z:
δ 139.0 (1C), 132.7 (1C), 130.5 (1C), 129.2 (1C), 128.5 (1C),
+
[M+H] Calcd for C
9
H
10
O
3
167.0703; found: 167.0694
125.9 (2C), 81.0 (1C), 29.2 (1C), 26.7 (1C), 18.4 (1C); IR
-1
cm : 3338, 3025, 2928, 2854, 1490, 1455, 2854, 1490, 1455,
+
4
1
-(5-(4-(hydroperoxymethyl)phenyl)-3-(trifluoromethyl)-
H-pyrazol-1-yl)benzenesulfonamide (2r). Flash column
1311, 1069, 947, 762, 741. HRMS (ESI) m/z: [M+H] Calcd
for C H O 165.0910; found: 165.0909
1
0
12
2
chromatography (2-5 % EtOAc/hexanes) to provide 2r as pale
1
yellow oil (53.2 mg, 43% yield). H NMR (400 MHz, CDCl
3
):
3,4-Dihydronaphthalen-1(2H)-one (2xb). Flash column
chromatography (2-5 % EtOAc/hexanes) to provide 2xb as
δ 8.20 (s, 1H), 7.91 (d, J = 8 Hz, 2H), 7.47 (d, J = 8 Hz, 2H),
1
7
5
.41 (d, J = 8 Hz, 2H), 7.25 (d, J = 8 Hz,2H), 6.79 (s, 1H),
colorless oil (29.2 mg, 20% yield). H NMR (400 MHz,
13
1
.03 (s, 2H),
4.94 (br, 2H). C{ H} NMR (101 MHz,
CDCl
3
): δ 8.03 (d, J = 8 Hz, 1H), 7.47 (t, J = 8 Hz, 1H), 7.31
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CDCl
): δ 143.7 (1C), 142.1 (1C), 142.0 (1C), 136.6 (1C),
(t, J = 8 Hz, 1H), 7.25 (d, J = 8 Hz, 1H), 2.97 (t, J = 8 Hz,
3
1
3
1
134.2 (1C), 130.2 (2C), 129.4 (2C), 129.3 (1C), 127.8 (2C),
2H), 2.66 (t, J = 8 Hz, 2H), 2.14 (m, 2H). C{ H} NMR (101
MHz, CDCl ): δ 198.4 (1C), 144.5 (1C), 133.4 (1C), 132.7
-1
127.6 (1C), 125.6 (2C), 107.4 (1C), 78.4 (1C) IR cm :
346, 3259, 3101, 2924, 2853, 1274, 1162. HRMS (ESI)
3
3
(1C), 128.8 (1C), 127.2 (1C), 126.6 (1C), 39.2 (1C), 29.7
+
-1
m/z: [M+H] Calcd for C17
14.0754
H
14
F
3
N
3
O
4
S 414.0730; found:
(1C), 23.3 (1C); IR cm : 3033, 2952, 1823, 1683, 1263, 1264,
+
4
1013, 932, 798, 698, 353. HRMS (ESI) m/z: [M+H] Calcd for
10
C H10O 147.0804; found: 147.0819
(E)-ethyl 5-hydroperoxy-5-phenylpent-2-enoate (2va).
Flash column chromatography (2-5 % EtOAc/hexanes) to
4-Hydroperoxy-3,4-dihydronaphthalen-1(2H)-one
(2xc).
1
provide 2va as yellow oil (54.2 mg, 46% yield). H NMR (400
MHz, CDCl ): δ 8.01 (s, 1H), 7.34-7.20 (m, 5H), 6.91 (dd, J
Flash column chromatography (2-5 % EtOAc/hexanes) to
1
3
provide 2xc as colorless oil (55.1mg, 31% yield). H NMR
(400 MHz, CDCl ): δ 8.57 (s, 1H), 8.03 (d, J = 8 Hz, 1H),
7.61-7.45 (m, 3H), 5.19 (t, J = 4 Hz, 1H), 2.98-2.89 (m, 1H),
= 8 Hz, 1H), 6.01 (d, J = 8 Hz, 1H), 4.75 (q, J = 8 Hz, 1H),
3
4.21 (q, J = 8 Hz, 2H), 3.01 (dd, J = 8 Hz, 1H), 2.86 (dd, J =
Hz, 1H), 1.29 (t, J = 8 Hz, 3H) 13C{ H} NMR (101 MHz,
1
2.68-2.56 (m, 2H), 2.38-2.29 (m, 1H) C{ H} NMR (101
MHz, CDCl ): δ 197.3 (1C), 139.06 (1C), 133.7 (1C), 132.5
(1C), 129.7 (1C), 129.5 (1C), 127.3 (2C), 80.1 (1C), 33.7
13
1
8
CDCl
3
): δ 165.9 (1C), 145.0 (1C), 136.3 (1C), 129.4 (2C),
3
1
3
1
28.5 (2C), 126.8 (1C), 123.8 (1C), 85.3 (1C), 60.6 (1C),
-1
8.8 (1C), 14.2 (1C) IR:3370, 3064, 2924, 1718, 1710, 1370,
(1C), 26.3 (1C); IR cm : 3327, 2957, 1672, 1334, 1209, 1188,
+
+
306, 1277, 1178, 1031,700. HRMS (ESI) m/z: [M+H] Calcd
1045, 945, 770, 721. HRMS (ESI) m/z: [M+H] Calcd for
for C13
H
16
O
4
237.1121; found: 237.1110
10 12 2
C H O 179.0703; found: 179.0713
(1-Hydroperoxypropane-1,3-diyl)dibenzene (2wa). Flash
2-Ethylbenzoic acid (2ya). Flash column chromatography (2-
column chromatography (2-5 % EtOAc/hexanes) to provide
2wa as colorless oil (62.7 mg, 55% yield). 1H NMR (400
MHz, CDCl3): δ 7.43-7.35 (m, 5H), 7.31-28 (m, 2H), 7.22-
5 % EtOAc/hexanes) to provide 2ya as colorless oil (48.8 mg,
1
65% yield). H NMR (400 MHz, CDCl
3
): δ 8.04 (d, J = 8 Hz,
1H), 7.49 (t, J = 8 Hz, 1H), 7.31 (t, J = 8 Hz, 2H), 3.07 (q, J
1
3
1
7
2
.17 (m, 3H), 4.93 (t, J = 8 Hz, 1H), 2.75-2.64 (m, 2H),
.27-2.18 (m, 1H), 2.04-1.95 (m, 1H) C{ H} NMR (101
= 8 Hz, 2H), 1.27 (t, J = 8 Hz, 3H). C{ H} NMR (101 MHz,
CDCl ): δ 172.7 (1C), 147.3 (1C), 133.0 (1C), 131.6 (1C),
1
3
1
3
MHz, CDCl3): δ 141.3 (1C), 140.4 (1C), 128.7 (2C), 128.4
130.5 (1C), 127.9 (1C), 125.8 (1C), 27.7 (1C), 15.9 (1C) IR:
(2C), 128.9 (4C), 126.0 (2C), 87.3 (1C), 35.9 (1C), 31.4
2928, 2357, 1694, 1602, 1456, 1404, 1300, 759, 744. HRMS
+
(
7
1C). IR: 3438, 3062, 2950, 1495, 1454, 1366, 1309, 1029,
(ESI) m/z: [M+H] Calcd for C
9
H
10
O
2
151.0754; found:
+
50, 698, 548. HRMS (ESI) m/z: [M+H] Calcd for C15
H
16
O
2
151.0786
+
[M+H] : 229.1223; found: 229.1254
tert-Butyl((1,2-diphenylethyl)peroxy)dimethylsilane (3aa).
1,3-Dihydroperoxy-1,3-diphenylpropane
column chromatography (2-5 % EtOAc/hexanes) to provide
wb as colorless oil (27.3 mg, 55% yield, cis : trans
(2wb)
Flash
Flash column chromatography (2-5 % EtOAc/hexanes) to
1
provide 3aa as light yellow oil (42.0 mg, 85% yield).
NMR (400 MHz, CDCl
5.00 (t, J = 8 Hz, 1H), 3.25 (m, 1H), 2.97 (m, 1H), 0.88 (s,
H
2
3
): δ 7.32-7.18 (m, 8H), 7.10 (m, 2H),
1
dihydroperoxide = 1 : 1 ). H NMR (400 MHz, CDCl
2H), 7.39-7.34 (m, 20H), 5.15 (t, J = 8 Hz, 2H), 4.95 (t, J = 8
Hz, 2H), 2.61-2.54 (m, 1H), 2.22 (m, 2H), 2.02-1.95 (m, 1H).
3
): δ 7.98
1
3
1
(
9H), 0.01 (s, 3H), 0.00 (s, 3H). C{ H} NMR (101 MHz,
CDCl ): δ 140.3 (1C), 137.7 (1C), 129.6 (4C), 128.1 (4C),
3
1
3
1
C{ H} NMR (101 MHz, CDCl
28.8 (8C), 127.0 (8C), 126.9 (4C), 84.9 (2C), 84.2 (2C), 39.2
1C), 38.6 (1C). IR: 3375, 3076, 2924, 1495, 1456, 1372,
3
): δ 139.9 (2C), 139.6 (2C),
127.2 (2C), 88.8 (1C), 41.31 (1C), 26.2 (3C), 18.2 (1C), -
5.9 (2C) IR: 2928, 1455, 1250, 834, 784, 755, 697. HRMS
1
(
+
+
(ESI) m/z: [M+H] Calcd for C20
H
28
O
2
Si [M+H] : 329.1931;
+
1
334, 1062, 1028, 754, 700, 609. HRMS (ESI) m/z: [M+H]
261.1121; found: 261.1327
found: 329.1834
16 4
Calcd for C15H O
(Benzhydrylperoxy)(tert-butyl)dimethylsilane (3na) Flash
1
-Hydroperoxy-1,2,3,4-tetrahydronaphthalene (2xa). Flash
column chromatography (2-5 % EtOAc/hexanes) to provide
1
column chromatography (2-5 % EtOAc/hexanes) to provide
3na as colorless oil (37.7 mg, 80% yield). H NMR (400
1
2
xa as colorless oil (16.4 mg, 10% yield). H NMR (400 MHz,
CDCl ): δ 7.42 (d, J = 8 Hz, 1H), 7.26 (m, 1H), 7.21 (m, 1H),
.13 (d, J = 8 Hz, 1H), 5.05 (t, J = 4 Hz, 1H), 2.87-2.80 (m,
H), 2.78-2.65 (m, 1H), 2.42-2.36 (m, 1H), 2.02-1.89 (m,
3
MHz, CDCl ): δ 7.33 (m, 10 H), 5.95 (s, 1H), 0.91 (s, 9H),
1
3
1
3
0.12 (s, 6H). C{ H} NMR (101 MHz, CDCl
3
): δ 140.0 (2C),
7
1
132.4 (2C), 130.1 (2C), 128.2 (3C), 127.7 (3C), 89.0 (1C),
-1
26.2 (3C), 18.3 (1C), -5.68 (2C). IR cm : 2928, 2856, 1453,
6
ACS Paragon Plus Environment