PAPER
Directed ortho Metallation Chemistry and Phosphine Synthesis
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13C NMR (75 MHz, CDCl3): d = 143.6 (dd, J = 30.2, 12.1 Hz, 1 C),
139.9 (dd, J = 122.8, 29.1 Hz, 1 C), 135.1 (d, 1 C, J = 128.3), 133.6
(d, J = 13.1 Hz, 1 C), 133.2 (dd, J = 12.6, 8.6 Hz, 1 C), 132.9 (2 × d,
J = 9.6, 9.1 Hz, 2 C), 130.7 (d, J = 2.5 Hz, 1 C), 130.0 (d, J = 2.6
Hz, 1 C), 127.7 (d, J = 12.6 Hz, 2 C), 127.2 (d, J = 12.6 Hz, 1 C),
54.7 (s, 2 C), 35.3 (dd, J = 16.7, 7.5 Hz, 2 C), 30.8–26.8 (m, 10 C),
26.3 (s, 2 C), 20.8 (s, 2 C), 20.4 (s, 2 C).
2 C), 23.2 (t, J = 5.0 Hz, 4 C), 21.5 (d, J = 23.1 Hz, 1 C), 20.9 (d,
J = 20.9 Hz, 1 C).
31P NMR (121 MHz, CDCl3): d = 33.2 (d, J = 9.4 Hz, 1 P), –25.0 (br
s, 1 P).
HRMS (EI, 70 eV): m/z calcd for C32H37NOP2: 513.2359; found:
513.2350.
31P NMR (121 MHz, CDCl3): d = 33.9 (d, J = 10.7 Hz, 1 P), –9.6 (br
P-{2-[Bis(2-ethylphenyl)phosphino]phenyl}-N,N-diethyl-P-
phenylphosphinic Amide (2i)
Compound 2i was synthesised from 1a (500 mg, 1.83 mmol) and (2-
EtC6H4)2PCl (3.66 mmol, 2 equiv). Addition of the anion soln to a
soln of the electrophile in THF (10 mL) was needed to increase the
yield of the product. Extraction and chromatography were per-
formed as described in the above general procedure.
s, 1 P).
MS (CI): m/z (%) = 526 (100) [M + H]+, 442 (75), 397 (50).
HRMS (EI, 70 eV): m/z calcd for C32H48NOP2: 525.3211; found:
525.3186.
P-{2-[Bis(2-methylphenyl)phosphino]phenyl}-N,N-diethyl-P-
phenylphosphinic Amide (2g)
Yield: 62%; white foam; Rf = 0.43 (hexanes–EtOAc, 1:1)
Compound 2g was synthesised from 1a (300 mg, 1.10 mmol) and
(2-MeC6H4)2PCl (1.2 mmol). Addition of the anion soln to a soln of
the electrophile (2-MeC6H4)2PCl in THF (10 mL) was needed to in-
crease the yield of the product. Extraction and chromatography
were performed as described in the above general procedure.
IR (CHCl3): 3007, 1185, 754 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.93–7.86 (m, 1 H), 7.64–7.58 (m,
2 H), 7.36–7.02 (m, 10 H), 6.96–6.91 (m, 1 H), 6.85 (t, J = 7.2 Hz,
1 H), 6.69–6.62 (m, 2 H), 3.06–2.88 (m, 4 H), 2.73–2.55 (m, 2 H),
2.43–2.33 (m, 2 H), 1.05 (t, J = 7.5 Hz, 3 H), 1.01 (t, J = 7.1 Hz, 6
H), 0.85 (t, J = 7.5 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 147.8 (dd, J = 17.9, 17.4 Hz, 2 C),
142.8 (dd, J = 12.8, 12.8 Hz, 1 C), 138.2 (dd, J = 30.0, 29.5 Hz, 1
C), 136.5 (d, J = 12.5 Hz, 2 C), 136.2 (d, J = 15.1 Hz, 1 C), 135.7
(d, J = 14.5 Hz, 2 C), 133.5 (d, J = 17.3 Hz, 2 C), 133.2 (d, J = 17.1
Hz, 2 C), 132.9 (d, J = 124.4 Hz, 1 C), 131.9 (dd, J = 8.9, 9.5 Hz, 2
C), 130.6 (dd, J = 22.5, 19.7 Hz, 1 C), 128.1 (d, J = 3.0 Hz, 2 C),
127.6 (d, J = 5.3 Hz, 2 C), 127.3 (d, J = 12.8 Hz, 2 C), 125.2 (d,
J = 10.5 Hz, 2 C), 39.1 (d, J = 3.5 Hz, 2 C), 26.9 (2xd, J = 14.9, 15.9
Hz, 2 C), 14.6 (d, J = 3.9 Hz, 2 C), 13.7 (d, J = 3.38 Hz, 2 C).
Yield: 48%; pale yellow foam; Rf = 0.52 (hexanes–EtOAc, 10:1).
IR (CHCl3): 3022, 1203, 667 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.96–7.88 (m, 1 H), 7.61–7.55 (m,
1 H), 7.43–6.88 (m, 14 H), 6.60–6.57 (m, 1 H), 3.11–2.93 (m, 4 H),
2.26 (s, 3 H), 2.02 (s, 3 H), 1.01 (t, J = 7.2 Hz, 6 H).
13C NMR (75 MHz, CDCl3): d = 142.8 (dd, J = 27.2, 17.5 Hz, 1 C),
142.0 (dd, J = 37.6, 12.8 Hz, 2 C), 138.3 (dd, J = 125.2, 29.3 Hz, 1
C), 136.2 (dd, J = 46.8, 14.4 Hz, 2 C), 136.2 (dd, J = 23.5, 12.2 Hz,
1 C), 133.5 (dd, J = 10.3, 7.4 Hz, 2 C), 133.5 (d, J = 7.4 Hz, 2 C),
133.3 (s, 1 C), 133.0 (d, J = 125.8 Hz, 1 C), 132.0 (dd, J = 9.4, 2.6
Hz, 2 C), 131.1 (d, J = 2.6 Hz, 1 C), 130.5 (d, J = 2.6 Hz, 1 C), 129.8
(dd, J = 8.7, 4.4 Hz, 2 C), 128.0 (d, J = 3.2 Hz, 2 C), 128.0 (d,
J = 11.9 Hz, 1 C), 127.5 (d, J = 12.5 Hz, 2 C), 125.5 (d, J = 5.7 Hz,
2 C), 39.3 (d, J = 3.5 Hz, 2 C), 21.3 (d, J = 22.2 Hz, 1 C), 20.9 (d,
J = 21.1 Hz, 1 C), 13.9 (d, J = 5.4 Hz, 2 C).
31P NMR (121 MHz, CDCl3): d = 33.6 (d, J = 4.5 Hz, 1 P), –27.3 (d,
J = 4.6 Hz, 1 P).
HRMS (EI, 70 eV): m/z calcd for C32H37NOP2: 513.5972; found:
513.5803.
31P NMR (121 MHz, CDCl3): d = 33.2 (d, J = 5.0 Hz, 1 P), –24.9 (d,
J = 5.0 Hz, 1 P).
P-{2-[Bis(2,3-dimethylphenyl)phosphino]phenyl}-N,N-diethyl-
P-phenylphosphinic Amide (2j)
Compound 2j was synthesised from 1a (300 mg, 1.10 mmol) and o-
xylyl2PCl (3.66 mmol). Addition of the anion soln to a soln of the
electrophile in THF (10 mL) was needed to increase the yield of the
product. Extraction and chromatography were performed as de-
scribed in the above general procedure.
HRMS (EI, 70 eV): m/z calcd for C30H33NOP2: 485.2028; found:
485.2037.
P-{2-[Bis(2-methylphenyl)phosphino]phenyl}-N,N-diisopropyl-
P-phenylphosphinic Amide (2h)
Compound 2h was synthesised from 1b (300 mg, 1.00 mmol) and
(2-MeC6H4)2PCl (1.2 mmol). Addition of the anion soln to a soln of
the electrophile (2-MeC6H4)2PCl in THF (10 mL) was needed to in-
crease the yield of the product. Extraction and chromatography
were performed as described in the above general procedure.
Yield: 58%; pale yellow foam; Rf = 0.48 (hexanes–EtOAc, 7:3).
IR (CHCl3): 3030, 1206, 710 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.95–7.87 (m, 1 H), 7.60–7.53 (m,
2 H), 7.44–7.00 (m, 9 H), 6.90–6.79 (m, 2 H), 6.45–6.12 (m, 2 H),
3.13–2.95 (m, 4 H), 2.19 (d, J = 12.3 Hz, 12 H), 1.02 (t, J = 3.4 Hz,
6 H).
13C NMR (75 MHz, CDCl3): d = 140.5 (dd, J = 24.2, 18.6 Hz, 2 C),
136.8 (dd, J = 37.6, 12.8 Hz, 2 C), 133.4 (d, J = 46.4, 27.3 Hz, 2 C),
132.2 (d, J = 49.7 Hz, 1 C), 131.5 (dd, J = 32.2, 12.2 Hz, 2 C), 131.3
(d, J = 21.5, 7.4 Hz, 2 C), 131.1 (d, J = 7.3 Hz, 2 C), 130.6 (d,
J = 30.2 Hz, 1 C), 129.9 (d, J = 125.8 Hz, 1 C), 129.3 (d, J = 2.6 Hz,
2 C), 128.0 (d, J = 2.6 Hz, 2 C), 127.6 (d, J = 2.6 Hz, 2 C) ,127.5 (d,
J = 2.6 Hz, 2 C), 125.7 (d, J = 4.2 Hz, 2 C), 125.3 (d, J = 4.6 Hz, 1
C), 125.2 (d, J = 12.5 Hz, 2 C), 121.9 (d, J = 5.7 Hz, 1 C), 39.4 (d,
J = 7.5 Hz, 2 C), 20.6 (d, J = 22.4 Hz, 1 C), 17.9 (d, 1 C, J = 25.0),
17.1 (d, J = 27.6 Hz, 1 C), 17.0 (d, 1 C, J = 26.7), 13.9 (d, J = 3.15
Hz, 2 C).
Yield: 48%; pale yellow foam; Rf = 0.45 (hexanes–EtOAc, 7:3).
IR (CHCl3): 3026, 1212, 793 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.96–7.89 (m, 1 H), 7.41–6.81 (m,
1 H), 6.60–6.57 (m, 14 H), 6.46–6.42 (m, 1 H), 3.41–3.31 (m, 2 H),
2.11 (s, 3 H), 1.77 (s, 3 H), 1.18 (d, J = 6.6 Hz, 6 H), 0.98 (d, J = 6.9
Hz, 6 H).
13C NMR (75 MHz, CDCl3): d = 142.4 (dd, J = 40.4, 27.0 Hz, 1 C),
141.4 (dd, J = 27.0, 23.9 Hz, 2 C), 140.5 (dd, J = 134.6, 27.1 Hz, 1
C), 137.1 (d, J = 10.6 Hz, 1 C), 136.4 (dd, J = 100.2, 12.3 Hz, 2 C),
135.5 (d, J = 119.8 Hz, 1 C), 133.4 (s, 1 C), 132.6 (s, 1 C), 132.9
(dd, J = 10.3, 7.8 Hz, 2 C), 131.6 (d, J = 9.7 Hz, 2 C), 131.0 (d,
J = 2.9 Hz, 1 C), 130.2 (d, J = 2.6 Hz, 1 C), 129.8 (dd, J = 9.1, 4.3
Hz, 2 C), 128.0 (d, 2 C, 11.4 Hz), 127.8 (d, J = 10.8 Hz, 1 C), 127.3
(d, J = 12.2 Hz, 2 C), 125.4 (d, J = 2.0 Hz, 2 C), 47.0 (d, J = 4.6 Hz,
31P NMR (121 MHz, CDCl3): d = 34.1 (d, J = 6.1 Hz, 1 P), –23.5 (d,
J = 5.3 Hz, 1 P).
Synthesis 2009, No. 18, 3106–3112 © Thieme Stuttgart · New York