B. Heller et al.
1
tate 1:1); H NMR (CDCl3): d = 7.97–7.92
C21H25N2O2P: 368.41; found: 368 (100) [M]+, 337 (74), 324 (57), 309 (16),
294 (70), 279 (88), 266 (62), 249 (52), 232 (15), 215 (35), 202 (31), 189
(32), 169 (14).
(m, 1H), 7.53–7.41 (m, 4H), 7.28–7.23 (m,
2H), 7.1–7.0 (m, 5H), 6.9–6.87 (m, 2H),
6.58–6.55 (m, 2H), 6.32–6.29 ppm (m, 2H);
1-[2-(Diphenylphosphinoyl)-3,4,5,6-tetramethylphenyl]naphthalene (19):
13C NMR (CDCl3):
d = 162.0 (d, J =
M.p. 194–1958C (ethyl acetate/hexane); Rf
= 0.45 (ethyl acetate);
1H NMR (CDCl3): d = 7.7–7.68 (m, 1H), 7.62–
7.58 (m, 2H), 7.52–7.49 (m, 2H), 7.45–7.39 (m,
6H), 7.29–7.25 (m, 1H), 7.19–7.14 (m, 3H),
7.07–7.03 (m, 2H), 2.63 (s, 3H), 2.57 (s, 3H),
2.54 (s, 3H), 1.84 ppm (s, 3H); 13C NMR
(CDCl3): d = 141.3, 141.2, 140.6, 140.5, 139.8,
139.8, 139.4, 139.4, 137.8, 137.1, 137.0, 136.8,
135.4, 134.4, 134.3, 134.2, 133.2, 132.7, 131.3,
131.2, 130.8, 130.7, 130.5, 129.9, 129.8, 129.7,
2.9 Hz), 161.5 (d, J = 2.9 Hz), 154.1, 140.9,
140.8, 134.9, 134.87, 134.0, 133.9, 133.8,
133.6, 133.4, 133.2, 133.1, 132.0, 132.0,
129.9, 128.7, 127.7, 127.6, 126.3, 125.9,
125.8, 125.0, 124.7, 123.9, 123.4, 123.3,
123.2, 113.6, 113.5, 113.1, 113.0, 112.5, 56.0,
55.6, 55.4 ppm; 31P NMR (CDCl3): d = 28.3 ppm; MS (70 eV): m/z: 494
(100) [M]+, 463 (89), 357 (67), 337 (50), 263 (64), 247 (24), 232 (56), 214
(41), 189 (27), 155 (17), 108 (16), 77 (13).
1-(2-{Bis-[3,5-bis-(trifluoromethyl)phenyl]phosphinoyl}phenyl)-2-methox-
ynaphthalene (15): M.p. 154–1558C (ethyl acetate/hexane); Rf = 0.79
129.7, 129.4, 129.4, 128.9, 128.3, 127.5, 127.4, 127.3, 127.2, 127.1, 126.0,
125.7, 125.4, 22.4 (d, J = 6.7 Hz), 18.2 (d, J = 1.9 Hz), 17.8, 17.0 ppm;
1H NMR
31P NMR (CDCl3): d
= 30.6 ppm; HRMS: m/z: calcd for C32H28OP:
(hexane/ethyl
(CDCl3): d = 7.84–7.78 (m, 3H), 7.72–7.65
(m, 4H), 7.59–7.52 (m, 2H), 7.5 (d, J
8.9 Hz, 1H), 7.43–7.40 (m, 1H), 7.28–7.25 (m,
1H), 7.19–7.11 (m, 2H), 6.96 (d, J = 9.1 Hz,
acetate
4:1);
459.1872; found: 459.1861 (d = À2.5).
=
1-[2-(Diphenylphosphinoyl)phenyl]-2-methylnaphthalene (20): M.p. 163–
1648C (ethyl acetate/hexane); Rf
=
0.56 (ethyl acetate); 1H NMR
(CDCl3): d = 8.07–8.01 (m, 1H), 7.93–7.87 (m,
3H), 7.83–7.74 (m, 3H), 7.67–7.63 (m, 1H),
7.59–7.43 (m, 7H), 7.39–7.35 (m, 1H), 7.3–7.26
(m, 2H), 7.16–7.11 (m, 2H), 2.48 ppm (s, 3H);
1H), 6.92–6.90 (m, 1H), 3.73 ppm (s, 3H);
13C NMR (CDCl3): d = 154.9, 141.4, 141.3,
136.4, 135.6, 135.3, 134.6, 134.4, 134.3, 134.1,
134.0, 133.8, 133.6, 133.3, 132.1, 132.0, 131.8,
131.6, 131.5, 131.4, 131.3, 131.2, 130.5, 128.6,
128.5, 128.1, 127.9, 127.6, 125.7, 124.7, 124.3,
13C NMR (CDCl3):
d = 144.7, 144.6, 136.0,
136.0, 135.5, 134.8, 134.7, 134.0, 133.9, 133.0,
132.9, 132.7, 132.5, 132.4, 132.4, 132.2, 132.1,
131.7, 131.6, 131.6, 131.2, 131.1, 130.7, 130.7,
128.5, 128.4, 128.3, 128.2, 127.8, 127.6, 127.6,
127.5, 127.4, 126.5, 125.6, 124.6, 21.8 ppm;
124.3, 122.0, 121.9, 121.6, 121.6, 112.6, 56.4 ppm; 31P NMR (CDCl3): d =
23.1 ppm; HRMS: m/z: calcd for C33H19O2F12P: 706.0926; found:
706.0941 (d = 2.1).
1-[2-(Di-tert-butylphosphinoyl)phenyl]-2-methoxynaphthalene (16): M.p.
215–2168C (ethyl acetate/hexane); Rf = 0.51 (THF); 1H NMR (CDCl3):
d = 7.76 (d, J = 9.1 Hz, 1H), 7.69–7.64 (m,
31P NMR (CDCl3): d
= 26.1 ppm; HRMS: m/z: calcd for C29H23OP:
418.1481; found: 418.1472 (d = À2.2).
IV) Three-compound [2+2+2] cycloaddition
2H), 7.52–7.47 (m, 1H), 7.39–7.34 (m, 1H),
4,5-Diethyl-3-(2-methoxy-1-naphthyl)-6-phenyl-2-pyridyl-
7.26–7.03 (m, 5H), 3.72 (s, 3H), 1.22 (d, J =
AHCTREUNG
13.1 Hz, 1H), 0.99 ppm (d, J = 13.5 Hz, 1H);
13C NMR (CDCl3): d
= 154.0, 144.3, 144.2,
136.1, 134.7, 134.6, 134.1, 132.3, 132.3, 132.2,
131.6, 130.8, 130.8, 129.4, 128.8, 128.3, 126.2,
125.8, 125.7, 125.2, 124.9, 124.8, 122.8, 116.7,
112.5, 55.8, 38.2 (d, J = 6.7 Hz), 37.7 (d, J =
5.7 Hz), 28.7 ppm (d, J = 40 Hz); 31P NMR (CDCl3): d = 52.9 ppm;
HRMS: m/z: calcd for C25H31O2P: 394.2056; found: 394.2053 (d = À0.9).
1-[2-(Di-1-adamantylphosphinoyl)phenyl]-2-methoxynaphthalene
M.p. >3008C (ethyl acetate/hexane); Rf = 0.69 (ethyl acetate); H NMR
(CDCl3): d = 8.06 (d, J = 9.1 Hz, 1H), 7.99–
(17):
1
7.92 (m, 2H), 7.84–7.80 (m, 1H), 7.72–7.67 (m,
1H), 7.56–7.45 (m, 2H), 7.41–7.33 ppm (m,
3H); 13C NMR (CDCl3): d = 153.9, 144.7 (d, J
naphthalene (382 mg, 1 mmol) and [cpCo(cod)](11.6 mg, 0.05 mmol).
A
=
3.8 Hz), 134.7, 134.6, 134.1, 132.2, 132.1,
THF (10 mL) was added, followed by hex-3-yne (115 mL, 1 mmol) and
benzonitrile (103 mL, 1 mmol), and the mixture was stirred and irradiated
with two 460 W lamps (lꢀ420 nm) for 24 h. The reaction was quenched
by switching off the lamps and simultaneously opening the vessel to the
air, the sample was analyzed by GC, the solvent was evaporated, and the
residue was purified on silica gel (THF/hexane 1:1) to give compound 21
(217 mg, 38%).
131.0, 130.6, 130.6, 130.2, 129.3, 128.8, 128.2,
126.3, 125.5, 125.4, 124.9, 124.9, 124.9, 122.7,
112.4, 55.8, 42.5, 42.3, 41.9, 41.7, 38.1, 38.1, 37.7,
37.6, 37.2, 37.0, 28.7, 28.6, 28.3, 28.2 ppm;
31P NMR (CDCl3): d = 44.6 ppm; HRMS: m/z:
calcd for C37H43O2P: 550.2995; found: 550.2985
(d = À1.8).
Compound 21: M.p. 208–2098C (ethyl acetate/hexane); 1H NMR
(CDCl3): d = 8.1 (d, J = 8.9 Hz, 1H), 8.0–7.93 (m, 3H), 7.8–7.55 (m,
8H), 7.51–7.44 (m, 5H), 7.38–7.33 (m, 3H), 7.2 (d, J = 8.3 Hz, 1H),
3.11–3.01 (m, 2H), 2.74–2.65 (m, 1H), 2.57–2.49 (m, 1H), 1.31 (t, J =
1-[2-(Bis-dimethylaminophosphinoyl)phenyl]-2-methoxynaphthalene
(18): Rf = 0.43 (THF); 1H NMR (CDCl3): d = 8.35–8.30 (m, 1H), 8.11
(d, J = 8.9 Hz, 1H), 8.06–8.04 (m, 1H), 7.83–7.72 (m, 2H), 7.6 (d, J =
9.1 Hz, 1H), 7.55–7.45 (m, 3H), 7.37–7.35 (m, 1H), 4.09 (s, 3H), 2.49 (d,
J = 9.5 Hz, 6H), 2.33 ppm (d, J = 9.7 Hz, 6H); 13C NMR (CDCl3): d =
7.5 Hz, 3H), 1.07 ppm (t, J
= =
7.5 Hz, 3H); 13C NMR (CDCl3): d
158.3, 158.1, 155.3, 153.2, 153.1, 152.1, 150.8, 141.6, 137.5, 137.5, 137.2,
137.0, 135.7, 134.9, 134.7, 134.3, 133.9, 132.7, 132.6, 132.5, 132.4, 130.9,
130.9, 130.8, 130.8, 130.5, 129.6, 128.9, 128.4, 128.2, 128.0, 127.8, 127.7,
127.7, 127.6, 126.5, 124.9, 123.4, 119.2, 113.0, 56.1, 23.4, 22.6, 15.7,
154.3, 141.1 (d,
J = 8.6 Hz), 135.3, 135.2,
134.4, 133.7, 133.0, 132.9, 132.2, 131.3, 131.3,
129.3, 129.0, 128.1, 127.4, 127.3, 126.2, 125.9,
125.8, 125.4, 125.4, 123.5, 113.6, 56.6, 36.5 ppm
14.6 ppm; 31P NMR (CDCl3): d
C38H34O2NP: 567.2322; found: 567.2330 (d = 1.4).
= 20.7 ppm; HRMS: m/z: calcd for
(q,
29.6 ppm; MS (70 eV): m/z: calcd for
J = d =
3.81 Hz); 31P NMR (CDCl3):
1124
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 1117 – 1128