Page 5 of 8
The Journal of Organic Chemistry
56.2 °C. 31P { H} NMR (121 MHz, CDCl
1
) δ: 45.47. H NMR
1
5i: The general procedure was followed using 506 mg 1i (2 mmol),
1
3
1
2
3
4
5
6
7
8
9
(300 MHz, CDCl
3
) δ: 7.82-7.75 (m, 1H), 7.64-7.53 (m, 2H), 7.50-
1.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane) and 181mg 3a (1
mmol). Purification by column chromatography (DCM: EA = 5: 1)
afforded 5i as pain yellow solid (171 mg, 55% yield). m p: 70.4-
7
.35 (m, 9H), 7.31-7.23 (m, 2H), 3.60-3.20 (m, 2H), 2.37 (s, 3H).
1
3
1
2
C { H} NMR (75 MHz, CDCl
3
) δ: 143.9 (d, JPC = 24.6 Hz, C),
3
4
31
1
1
1
39.8 (d, JPC = 10.9 Hz, C), 136.7 (s, C), 134.4 (d, JPC = 2.5 Hz,
72.3 °C. P { H} NMR (121 MHz, CDCl
MHz, CDCl ) δ: 7.79-7.65 (m, 2H), 7.64-7.53 (m, 3H), 7.53-7.36
(m, 4H), 5.92 (s, 1H), 3.58-3.07 (m, 2H), 0.25 (s, 9H). C { H}
3
) δ: 37.24. H NMR (300
1
1
CH), 133.7 (d, JPC = 98.0 Hz, C), 133.0 (d, JPC = 99.8 Hz, C),
3
2
4
13
1
1
J
32.5 (d, JPC = 7.0 Hz, C), 131.9 (d, JPC = 3.0 Hz, CH), 130.5 (d,
3
3
2
PC = 10.4 Hz, 2CH), 129.2 (d, JPC = 8.3 Hz, CH), 129.0 (s, 2CH),
3
NMR (75 MHz, CDCl ) δ : 147.4 (d, JPC = 5.9 Hz, C), 145.4 (d,
2
2
1
1
128.7 (d, JPC = 12.0 Hz, 2CH), 128.7 (s, 2CH), 127.6 (s, CH),
124.6 (d, JPC = 10.9 Hz, CH), 121.5 (d, JPC = 12.9 Hz, CH), 35.0
JPC = 20.4 Hz, C), 136.3 (d, JPC = 98.8 Hz, C), 132.6 (d, JPC =
3
2
4
4
99.0 Hz, C), 132.1 (d, JPC = 2.1 Hz, CH), 131.9 (d, JPC = 3.0 Hz,
CH), 130.6 (d, JPC = 10.3 Hz, 2CH), 129.6 (d, JPC = 10.8 Hz, CH),
129.3 (d, JPC = 5.4 Hz, CH), 129.2 (d, JPC = 7.6 Hz, CH), 128.6
1
+
3
2
(d, JPC = 71.1 Hz, CH
2
), 21.3 (s, CH
3
). HRMS (ESI) m/z: [M+H]
3
3
Calcd for C22
H
20OP 331.1246; Found 331.1249.
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
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
2
3
(
d, JPC = 12.4 Hz, 2CH), 125.2 (d, JPC = 10.5 Hz, CH), 43.0 (d,
JPC = 69.7 Hz, CH ), 0.1 (s, 3CH ). HRMS (ESI) m/z: [M+Na]
1
+
5
f: The general procedure was followed using 650 mg 1f (2 mmol),
2
3
1
.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane) and 181 mg 3a (1
18 21
Calcd for C H OPSiNa 335.0991; Found 335.0995.
mmol). Purification by column chromatography (DCM: EA=5:1)
afforded 5f as pain yellow solid (272 mg, 71% yield). m p: 132.9-
5j: The general procedure was followed using 574 mg 1c (2 mmol),
1.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane) and 250 mg 3b (1
mmol). Purification by column chromatography (DCM: EA = 5: 1)
afforded 5j as white solid (248 mg, 53% yield). m p: 60.4-61.6 °C.
3
1
1
1
1
(
7
2
34.7 °C. P { H} NMR (121 MHz, CDCl
300 MHz, CDCl ) δ: 8.04-7.91 (m, 2H), 7.88-7.80 (m, 1H), 7.66-
.53 (m, 2H), 7.53-7.39 (m, 7H), 7.36-7.28 (m, 1H), 3.64-3.38 (m,
3
) δ: 44.04. H NMR
3
1
3
1
2
H). C { H} NMR (75 MHz, CDCl
3
) δ: 149.5 (d, JPC = 25.2 Hz,
This solid was recrystallized from the mixture of CH
2
Cl
2
/hexane
1
4
31
1
C), 135.9 (s, C), 134.1 (d, JPC = 98.6 Hz, C), 132.4 (d, JPC = 3.0
before submitted to NMR analysis. P { H} NMR (121 MHz,
1
2
1
Hz, CH), 132.0 (d, JPC = 100.5 Hz, C), 131.3 (d, JPC = 7.1 Hz, C),
3 3
CDCl ) δ: 52.59. H NMR (300 MHz, CDCl ) δ: 8.08-7.97 (m, 1H)
131.2 (dd, JFC =33.0 Hz, 2JPC =11 Hz, C), 130.5 (d, JPC = 10.5 Hz,
3
3
7.76-7.67 (m, 1H), 7.62-7.50 (m, 1H), 7.50-7.39 (m, 2H), 7.37-7.08
(m, 9H), 6.88-6.97 (m, 3H), 6.90-6.79 (m, 2H), 6.75-6.60 (m, 2H),
2
2
CH), 130.1-129.8 (m, CH), 129.3 (s, 2CH), 128.9 (d, JPC = 12.8
3
2
13
1
Hz, 2CH), 128.8 (s, 2CH), 128.5 (s, CH), 128.3 (d, JPC = 10.8 Hz,
4.89 (d, JPH = 19.6 Hz, 1H), 3.75 (s, 3H). C { H} NMR (75 MHz,
1
2
1
CH), 127.2 (q, JFC = 273.0 Hz, C), 126.9-126.2 (m, CH), 122.3 (d,
CDCl
3
) δ: 159.2 (s, C), 149.4 (d, JPC = 23.3 Hz, C), 149.0 (d, JPC
= 93.0 Hz, C), 136.8 (d, JPC = 4.1 Hz, C), 133.8 (d, JPC = 7.6 Hz,
C), 133.7 (d, JPC = 2.1 Hz, CH), 132.3 (d, JPC = 9.4 Hz, 2CH),
31.7 (d, JPC = 2.9 Hz, CH), 130.6 (s, 2CH), 130.5 (d, JPC = 96.0
Hz, C), 130.0 (d, J = 8.2 Hz, CH), 129.1 (d, J =11 Hz, CH),
PC PC
PC PC
129.0 (d, J =10.6 Hz, CH), 128.7 (s, CH), 128.6 (d, J = 3.0
Hz, 2CH), 128.0 (s, C), 127.6 (d, J = 12.3 Hz, 2CH), 126.3 (d,
JPC = 3.4 Hz, CH), 121.6 (d, J = 11.5 Hz, CH), 113.8 (s, 2CH),
3
1
2
2
J
PC = 11.8 Hz, CH), 35.0 (d, JPC = 71.3 Hz, CH
2
). HRMS (ESI)
+
4
3
m/z: [M+H] Calcd for C22
H
17
F
3
OP 385.0964; Found 385.0960.
4
1
1
3
2
5g: The general procedure was followed using 650 mg 1g (2 mmol),
.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane) and 181 mg 3a (1
3
4
1
2
mmol). Purification by column chromatography (DCM: EA = 5: 1)
PC
3
3
afforded 5g as pain yellow solid (265 mg, 69% yield). m p: 92.3-
PC
3
1
1
1
1
9
4.7°C. P { H} NMR (121 MHz, CDCl
3
) δ: 44.17. H NMR (300
55.2 (s, CH ), 52.9 (d, J = 66.0 Hz, CH). HRMS (ESI) m/z:
[M+H] Calcd for C H O P 423.1508; Found 423.1511.
28 24 2
3
PC
+
MHz, CDCl
3
) δ: 8.13 (s, 1H) 7.90-7.76 (m, 1H), 7.70-7.53 (m, 3H),
13
1
7
.53-7.36 (m, 8H), 7.36-7.28 (m, 1H), 3.67-3.32 (m, 2H). C { H}
2
NMR (75 MHz, CDCl
3
) δ: 146.9 (d, JPC = 25.0 Hz, C), 137.0 (d,
5k: The general procedure was followed using 526 mg 1k (2 mmol),
1.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane), and 181 mg 3a (1
mmol). Purification by column chromatography (DCM: EA = 5: 1)
1
2
4
J
PC = 96.9 Hz, C), 136.0 (s, C), 135.2 (dd, JFC = 32.4 Hz, JPC =
4
1
2
.2Hz, C), 132.4 (d, JPC = 2.9 Hz, CH), 132.0 (d, JPC = 101.3 Hz,
2
3
31
1
C), 131.7 (d, JPC = 6.1 Hz, C), 130.5 (d, JPC = 10.5 Hz, 2CH),
1
afforded 5k as yellow liquid (154 mg, 48% yield). P { H} NMR
3
2
1
30.1 (d, JPC = 8.6 Hz, CH), 129.2 (s, 2CH), 128.9 (d, JPC
=
3 3
(121 MHz, CDCl ) δ: 51.07. H NMR (300 MHz, CDCl ) δ: 7.70-
2
1
2.0Hz, 2CH), 128.8 (s, 2CH ), 128.4(s, CH), 127.4 (d, JPC = 10.7
7.58 (m, 2H), 7.51-7.31 (m, 7H), 7.29-7.21 (m, 1H), 6.80 (s, 1H),
3.31-3.03 (m, 2H), 2.69-2.57 (m, 2H), 2.57-2.22 (m, 2H), 1.29-1.20
1
Hz, CH), 127.2 (q, JFC = 271.5 Hz, C), 126.0-125.6 (m, CH),
1
13
1
118.9-118.4 (m, CH), 34.9 (d, JPC = 71.2 Hz , CH
2
). HRMS (ESI)
(m, 3H), 1.04-0.95 (m, 3H). C { H} NMR (75 MHz, CDCl
3
) δ:
+
2
1
m/z: [M+H] Calcd for C22H F OP 385.0964; Foun 385.0960.
17 3
158.3 (d, JPC = 22.6 Hz, C ) 137.9 (d, JPC = 90.3 Hz, C), 136.9 (s,
C), 135.1 (d, JPC = 12.7 Hz, C), 133.1 (d, JPC = 96.6 Hz, C), 131.7
(d, J = 3.0 Hz, CH), 130.6 (d, J = 10.2 Hz, 2CH), 129.0 (s,
PC PC
PC
2CH), 128.6 (d, J = 11.3 Hz, 2CH), 128.6 (s, 2CH), 127.5 (s,
2
1
4
3
5
h: The general procedure was followed using 574 mg 1h (2 mmol),
2
1
.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane) and 181 mg 3a (1
3
1
mmol). Purification by column chromatography (DCM: EA = 5: 1)
PC PC
CH), 125.1 (d, J = 11.5 Hz,CH), 33.1 (d, J = 71.3 Hz. CH2),
afforded 5h as white solid (183 mg, 53% yield). m p: 144.5-
2
), 13.9 (d, 3JPC = 2.2 Hz,
3 3
), 19.8 (s, CH
2
0.0 (d, JPC = 5.6 Hz, CH
), 13.7 (d, 3JPC = 1.5 Hz, CH
2
). HRMS (ESI) m/z: [M+H]
3
1
1
1
145.7 °C. P { H} NMR (121 MHz, CDCl
3
) δ: 44.29. H NMR
+
CH
Calcd for C21 24OP 323.1559; Found 323.1562.
2
(300 MHz, CDCl ) δ: 7.69-7.52 (m, 3H), 7.51-7.31 (m, 8H), 7.31-
3
H
7
.20 (m, 2H), 6.85-6.74 (m, 1H), 3.75 (s, 3H), 3.57-3.24 (m, 2H).
1
3
1
2
C { H} NMR (75 MHz, CDCl
3
) δ : 161.3 (d, JPC = 2.1 Hz, C),
5l: The general procedure was followed using 582 mg 1l (2 mmol),
1.25 mL n-BuLi (2.0 mmol, 1.6 M in hexane), and 181 mg 3a (1
mmol). Purification by column chromatography (DCM: EA = 5: 1)
2
4
1
48.7 (d, JPC = 22.0 Hz, C), 136.6 (s, C), 135.5 (d, JPC = 1.6 Hz,
1
2
CH), 133.0 (d, JPC = 103.5 Hz, C), 132.5 (d, JPC = 7.0 Hz, C),
4
3
31
1
1
31.7 (d, JPC = 2.9 Hz, CH), 130.3 (d, JPC = 10.8 Hz, 2CH), 129.1
afforded 5l as colorless liquid (185 mg, 53% yield). P { H} NMR
2
1
(s, 2CH), 128.6 (s, 2CH), 128.5 (d, JPC = 12.6 Hz, 2CH), 127.8 (s,
(121 MHz, CDCl ) δ: 51.57. H NMR (300 MHz, CDCl ) δ: 7.72-
3
3
3
1
CH), 126.0 (d, JPC = 11.7 Hz, CH), 120.6 (d, JPC = 99.4 Hz, C),
7.55 (m, 2H), 7.49-7.29 (m, 7H), 7.26-7.19 (m, 1H), 6.79 (s, 1H),
3.32-2.97 (m, 2H), 2.66-2.53 (m, 2H), 2.53-2.11 (m, 2H), 1.75-1.50
(m, 2H), 1.47-1.32 (m, 2H), 1.17-0.99 (m, 3H), 0.93-0.77 (m, 3H).
3
3
1
13.7 (d, JPC = 11.9 Hz, CH), 110.2 (d, JPC = 6.0 Hz, CH), 55.8
), 35.3 (d, 1JPC = 72.5 Hz, CH
P 347.1195; Found 347.1198.
+
(s, CH
3
2
). HRMS (ESI) m/z: [M+H]
Calcd for C22
H
20
O
2
13C {
1
H} NMR (75 MHz, CDCl ) δ: 157.0 (d, JPC = 22.9 Hz, C),
2
3
1
2
1
37.3 (d, JPC=89.3 Hz, C), 136.9 (s, C), 135.5 (d, JPC = 13.0 Hz,
5
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