π-Insertion Reactions of Benzynes into P=N and P=S Double Bonds
2
2
132.72 (d, JP,C = 10.6 Hz, C-o), 133.07 (d, JP,C = 8.2 Hz, C-3),
(vs), 911 (s), 732 (vs) cm–1. HRMS (ESI): calcd. for C27H27NOP
[M – OTf]+ 412.1825; found 412.1830.
2
134.56 (C-p), 137.08 (C-4), 137.72 (d, JP,C = 10.0 Hz, C-6), 145.55
(C-1Ј or C-1ЈЈ), 146.17 (C-1Ј or C-1ЈЈ), 151.90 (d, 2JP,C = 4.4 Hz, C-
2) ppm. 19F{1H} NMR (282 MHz, CDCl3, 25 °C): δ = –78.20 ppm.
31P{1H} NMR (121 MHz, CDCl3, 25 °C): δ = 20.81 ppm. IR (Nu-
P-{2-[(N-4-bromophenyl-N-Phenyl)amino]phenyl}-P,P-dimethyl-P-
phenylphosphonium Triflate (4e): The general procedure with 1i
(0.09 g, 0.3 mmol) in anhydrous CH3CN (5 mL), 2a (0.23 g,
0.78 mmol) in anhydrous CH3CN (10 mL), and CsF (0.14 g,
0.9 mmol) afforded 4e as a yellow solid, which was purified by flash
column chromatography [gradient eluents: chloroform/methanol
9:1 (v/v) then ethanol; Rf = 0.2, TLC, chloroform/methanol 9:1
(v/v)] and recrystallized from dichloromethane/diethyl ether; 0.14 g,
jol): ν = 1487 (m), 1261 (s), 1031 (m), 908 (vs), 733 (vs) cm–1.
˜
HRMS (ESI): calcd. for C31H26BrNP [M – OTf]+ 522.0981; found
522.0984.
P,P-Dimethyl-P-phenyl-P-[2-(N-phenyl-N-4-methylphenyl)amino]-
phenylphosphonium Triflate (4c): The general procedure with 1f
(0.07 g, 0.3 mmol) in anhydrous CH3CN (5 mL), 2a (0.23 g, 76%; white prisms; m.p. 163–165 °C. 1H NMR (400 MHz, CDCl3,
2
3
0.78 mmol) in anhydrous CH3CN (10 mL), and CsF (0.14 g,
0.9 mmol) afforded 4c as a white solid, which was purified by flash
column chromatography [gradient eluents: chloroform/methanol
9:1 (v/v) then ethanol; Rf = 0.33, TLC, chloroform/methanol 9:1
(v/v)] and recrystallized from dichloromethane/diethyl ether; 0.11 g,
65%; white prisms; m.p. 183–185 °C. 1H NMR (400 MHz, CDCl3,
25 °C): δ = 2.21 (s, 3 H, CH3), 2.32 [d, 2JP,H = 13.6 Hz, 6 H, P(CH3)
25 °C): δ = 2.39 [d, JP,H = 13.6 Hz, 6 H, P(CH3)2], 6.52 (d, JH,H
3
= 8.8 Hz, 2 H, Ar H), 6.69 (d, JH,H = 7.8 Hz, 2 H, Ar H), 6.96 (t,
3JH,H = 7.8 Hz, 1 H, Ar H), 7.11 (d, JH,H = 8.8 Hz, 2 H, Ar H),
3
7.13 (t, 3JH,H = 7.8 Hz, 2 H, Ar H), 7.22 (dd, 3JH,H = 7.7 Hz, JP,H
4
= 5.6 Hz, 1 H, Ar H), 7.36–7.39 (m, 4 H, Ar H), 7.50–7.57 (m, 1
3
3
H, Ar H), 7.62 (t, JH,H = 7.7 Hz, 1 H, Ar H), 7.75 (t, JH,H
=
3
3
7.7 Hz, 1 H, Ar H), 8.08 (dd, JP,H = 14.7 Hz, JH,H = 7.7 Hz, 1
3
3
2], 6.53 (d, JH,H = 8.2 Hz, 2 H, Ar H), 6.66 (d, JH,H = 8.4 Hz, 2
H, Ar H) ppm. 13C{1H} NMR (100 MHz, CDCl3, 25 °C): δ = 9.22
3
3
1
1
H, Ar H), 6.88 (d, JH,H = 8.2 Hz, 2 H, Ar H), 6.93 (t, JH,H
=
(d, JP, C = 55.8 Hz, PCH3), 10.53 (d, JP,C = 57.6 Hz, PCH3),
116.63 (C-4Ј), 118.53 (d, JP,C = 86.7 Hz, C-1 or C-i), 120.28 (d,
3
1
8.4 Hz, 1 H, Ar H), 7.11 (t, JH,H = 8.4 Hz, 2 H, Ar H), 7.23 (t,
3JH,H = 6.7 Hz, 1 H, Ar H), 7.38–7.45 (m, 4 H, Ar H), 7.51–7.59 1JP,C = 87.9 Hz, C-1 or C-i), 120.74 (q, 1JF,C = 320.5 Hz, CF3SO3),
3
3
(m, 2 H, Ar H), 7.72 (t, JH,H = 7.7 Hz, 1 H, Ar H), 7.98 (dd,
122.83 (C-2ЈЈ), 124.06 (C-2Ј), 124.36 (C-4ЈЈ), 128.20 (d, JP, C
=
3JP,H = 14.9 Hz, JH,H = 7.9 Hz, 1 H, Ar H) ppm. 13C{1H} NMR
12.9 Hz, C-5), 129.83 (C-3ЈЈ), 129.92 (d, JP, C = 13.1 Hz, C-m),
3
3
1
2
3
(100 MHz, CDCl3, 25 °C): δ = 9.96 [d, JP,C = 57.8 Hz, P(CH3)2],
130.83 (d, JP,C = 10.7 Hz, C-o), 132.48 (C-3Ј) 132.52 (d, JP,C
=
=
1
4
2
20.70 (CH3), 118.11 (d, JP,C = 86.8 Hz, C-1 or C-i), 120.62 (d, 8.2 Hz, C-3), 133.73 (d, JP,C = 3.0 Hz, C-p), 136.09 (d, JP,C
1JP,C = 88.5 Hz, C-1 or C-i), 120.78 (q, 1JF,C = 320.4 Hz, CF3SO3),
9.6 Hz, C-6), 136.82 (d, JP,C = 2.4 Hz, C-4), 145.80 (C-1Ј or C-
1ЈЈ), 146.46 (C-1Ј or C-1ЈЈ), 150.79 (d, JP,C = 3.9 Hz, C-2) ppm.
4
3
2
122.50 (C-2ЈЈ), 123.10 (C-2Ј), 123.72 (C-4ЈЈ), 127.57 (d, JP, C
=
12.5 Hz, C-5), 129.58 (C-3ЈЈ), 129.82 (d, JP, C = 13.1 Hz, C-m), 31P{1H} NMR (162 MHz, CDCl3, 25 °C): δ = 18.15 ppm. IR (Nu-
3
2
3
130.24 (C-3Ј), 130.96 (d, JP,C = 10.7 Hz, C-o), 132.36 (d, JP,C
8.0 Hz, C-3), 133.67 (d, JP,C = 3.0 Hz, C-p), 133.93 (C-4Ј), 135.92
(d, JP,C = 9.8 Hz, C-6), 136.63 (d, JP,C = 2.4 Hz, C-4), 144.32 (C- 460.0825.
=
jol): ν = 1487 (vs), 1260 (vs), 1031 (vs), 911 (s), 731 (vs) cm–1.
˜
4
HRMS (ESI): calcd. for C26H24BrNP [M –OTf]+ 460.0824; found
2
4
2
1Ј or C-1ЈЈ), 147.37 (C-1Ј or C-1ЈЈ), 151.83 (d, JP,C = 4.0 Hz, C-2)
ppm. 31P{1H} NMR (162 MHz, CDCl3, 25 °C): δ = 18.08 ppm. IR
P-{2-[(N-4-nitrophenyl-N-phenyl)amino]phenyl}-P,P-dimethyl-P-
(Nujol): ν = 1508 (s), 1259 (vs), 1030 (s), 933 (m), 734 (m) cm–1.
phenylphosphonium Triflate (4f): The general procedure with 1j
(0.08 g, 0.3 mmol) in anhydrous CH3CN (5 mL), 2a (0.23 g,
0.78 mmol) in anhydrous CH3CN (10 mL), and CsF (0.14 g,
0.9 mmol) afforded 4f as a yellow solid, which was purified by flash
column chromatography [gradient eluents: chloroform/methanol
9:1 (v/v) then ethanol; Rf = 0.2, TLC, chloroform/methanol 9:1 (v/
˜
HRMS (ESI): calcd. for C27H27NP [M – OTf]+ 396.1876; found
396.1876.
P,P-Dimethyl-P-phenyl-P-[2-(N-phenyl-N-4-methoxyphenyl)amino]-
phenylphosphonium Triflate (4d): The general procedure with 1g
(0.08 g, 0.3 mmol) in anhydrous CH3CN (5 mL), 2a (0.23 g, v)] and recrystallized from dichloromethane/diethyl ether; 0.12 g,
0.39 mmol) in anhydrous CH3CN (10 mL), and CsF (0.14 g,
0.9 mmol) afforded 4d as a white solid, which was purified by flash
column chromatography [gradient eluents: chloroform/methanol
9:1 (v/v) then ethanol; Rf = 0.3, TLC, chloroform/methanol 9:1 (v/
69%; white prisms; m.p. 124–126 °C. 1H NMR (400 MHz, CDCl3,
2
2
25 °C): δ = 2.34 (d, JP,H = 14.0 Hz, 3 H, PCH3), 2.47 (d, JP,H
=
13.6 Hz, 3 H, PCH3), 6.76 (d, 3JH,H = 9.2 Hz, 2 H, Ar H), 6.77 (d,
3
3JH,H = 8.1 Hz, 2 H, Ar H), 7.04 (t, JH,H = 7.4 Hz, 1 H, Ar H),
3
3
v)] and recrystallized from dichloromethane/diethyl ether; 0.12 g, 7.18 (dd, JH,H = 8.1 Hz, JH,H = 7.4 Hz, 2 H, Ar H), 7.28–7.40
72%; white prisms; m.p. 171–173 °C. 1H NMR (400 MHz, CDCl3,
(m, 5 H, Ar H), 7.44–7.50 (m, 1 H, Ar H), 7.72 (t, JH,H = 7.9 Hz,
3
2
3
3
25 °C): δ = 2.33 [d, JP,H = 13.6 Hz, 6 H, P(CH3)2], 3.72 (s, 3 H,
1 H, Ar H), 7.83 (t, JH,H = 7.9 Hz, 1 H, Ar H), 7.86 (d, JH,H =
3
3
3
OCH3), 6.56–6.64 (m, 6 H, Ar H), 6.92 (t, JH,H = 7.4 Hz, 1 H, Ar 9.2 Hz, 2 H, Ar H), 8.14 (ddd, JP,H = 14.8 Hz, JH,H = 7.9 Hz,
3
3
H), 7.10 (t, JH,H = 7.4 Hz, 2 H, Ar H), 7.22 (t, JH,H = 8.0 Hz, 1
4JH,H = 1.2 Hz, 1 H, Ar H) ppm. 13C{1H} NMR (100 MHz,
1
1
H, Ar H), 7.41–7.46 (m, 4 H, Ar H), 7.52–7.58 (m, 2 H, Ar H), CDCl3, 25 °C): δ = 9.33 (d, JP,C = 57.6 Hz, PCH3), 10.10 (d, JP,C
7.72 (t, 3JH,H = 8.0 Hz, 1 H, Ar H), 7.97 (dd, 3JP,H = 14.9 Hz, 3JH,H = 58.1 Hz, PCH3), 119.16 (d, JP,C = 86.4 Hz, C-1 or C-i), 120.06
1
= 8.0 Hz, 1 H, Ar H) ppm. 13C{1H} NMR (100 MHz, CDCl3, (d, JP,C = 87.5 Hz, C-1 or C-i), 120.31 (C-2Ј), 120.71 (q, JF,C
=
1
1
25 °C): δ = 9.96 [d, 1JP,C = 58.5 Hz, P(CH3)2], 55.51 (OCH3), 114.91 320.5 Hz, CF3SO3), 123.89 (C-2ЈЈ), 125.35 (C-3Ј), 125.80 (C-4ЈЈ),
1
1
3
3
(C-3Ј), 117.76 (d, JP,C = 86.9 Hz, C-1 or C-i), 120.73 (d, JP,C
=
129.30 (d, JP,C = 12.3 Hz, C-5), 129.86 (d, JP,C = 13.2 Hz, C-m),
1
2
3
88.4 Hz, C-1 or C-i), 120.78 (q, JF,C = 320.4 Hz, CF3SO3), 122.07 130.15 (C-3ЈЈ), 130.89 (d, JP,C = 10.7 Hz, C-o), 132.96 (d, JP,C
(C-2ЈЈ), 123.48 (C-4ЈЈ), 124.93 (C-2Ј), 127.36 (d, JP,C = 12.7 Hz, 7.9 Hz, C-3), 133.97 (d, JP,C = 2.4 Hz, C-p), 136.48 (d, JP,C
=
=
3
4
2
3
C-5), 129.58 (C-3ЈЈ), 129.84 (d, JP,C = 12.9 Hz, C-m), 130.93 (d, 9.4 Hz, C-6), 137.14 (C-4), 142.21 (C-4Ј), 144.35 (C-1ЈЈ), 149.22 (d,
2JP,C = 10.6 Hz, C-o), 132.09 (d, JP,C = 8.0 Hz, C-3), 133.80 (d,
2JP,C = 3.6 Hz, C-2), 152.19 (C-1Ј) ppm. 19F{1H} NMR (282 MHz,
3
4JP,C = 2.8 Hz, C-p), 135.90 (d, 2JP,C = 9.9 Hz, C-6), 136.62 (d, 4JP,C
CDCl3, 25 °C): δ = –78.30 ppm. 31P{1H} NMR (162 MHz, CDCl3,
2
= 2.1 Hz, C-4), 139.87 (C-1Ј), 147.79 (C-1ЈЈ), 152.02 (d, JP,C
=
25 °C): δ = 18.76 ppm. IR (Nujol): ν = 1492 (m), 1270 (s), 1031
˜
3.9 Hz, C-2), 156.41 (C-4Ј) ppm. 31P{1H} NMR (162 MHz, CDCl3, (m), 908 (vs), 732 (vs) cm–1. HRMS (ESI): calcd. for C26H24N2O2P
25 °C): δ = 18.08 ppm. IR (Nujol): ν = 1507 (s), 1260 (vs), 1031 [M – OTf]+ 427.1570; found 427.1581.
˜
Eur. J. Org. Chem. 2014, 1084–1095
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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