M. Hapke et al.
FULL PAPER
1-(2-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphoryl}-3,4,5,6-tetra-
phenylphenyl)-2-methoxynaphthalene (3c): Reacting tetracyclone (1,
0.5 mmol) and the alkyne 2c (0.5 mmol) in accordance to the General
Procedure furnished the desired compound 3c; yield 470 mg, 93%;
m.p. 306–307 °C. 1H NMR (300 MHz, CDCl3): δ = 7.70 (d, J =
11.0 Hz, 2 H, Ar-H), 7.61–7.49 (m, 4 H, Ar-H), 7.44 (s, 1 H, Ar-H),
7.38–7.27 (m, 2 H, Ar-H), 7.20–7.06 (m, 3 H, Ar-H), 6.83 (q, J =
8.4 Hz, 3 H, Ar-H), 6.75–6.54 (m, 12 H, Ar-H), 6.48–6.27 (m, 4 H,
Ar-H), 6.19 (dd, J = 7.4, 1.0 Hz, 1 H, Ar-H), 3.63 (s, 3 H, OCH3)
ppm. 13C NMR (75 MHz, CDCl3): δ = 154.1, 146.7, 146.6, 146.2,
146.1, 143.3, 143.2, 143.1, 142.9, 140.0, 139.8, 139.4, 139.2, 138.7,
138.4, 138.0, 137.8, 137.7, 133.2, 133.0, 132.5, 131.3, 130.9, 130.8,
130.5, 130.2, 129.9, 129.4, 128.9, 127.3, 126.7, 126.0, 125.9, 125.8,
125.7, 125.6, 125.2, 125.1, 124.4, 123.3, 123.0, 121.4, 120.8, 110.7,
54.9 ppm. 31P NMR (125 MHz, CDCl3): δ = 16.6 ppm. MS (70 eV):
m/z (%) = 1009 (100) [M+], 488 (15). C57H35F12O2P (1010.84): calcd.
C 67.73, H 3.49; found C 67.59, H 3.52.
Experimental Section
General: The NMR spectra were recorded on a Bruker ARX 300
spectrometer at 298 K. Chemical shifts are reported in ppm relative
1
to the H and 13C residue of the deuterated solvent. Mass spectra
were obtained with a Varian AMD-402 instrument at an ionizing
voltage of 70 eV. Relative intensities in percentages are given in pa-
rentheses. Melting points were measured with a Büchi 540 melting
point determination apparatus. Optical rotations were determined
on a Gyromat-HP polarimeter. In all cases the enantiomeric ex-
cesses were analyzed by HPLC with a Liquid Chromatograph 1090
equipped with DAD (Hewlett–Packard) and Chiralyser (IBZ Mess-
technik GmbH, Hannover). The alkyne starting materials 2a–e and
2i–l have been prepared after published procedures from 1-ethynyl-
2-methoxynaphthalene.[11b] The phosphane 2f was prepared follow-
ing the literature procedure.[15] The synthesis and characterization
of compounds 2g, 2h, 4, 6 and the product 5 as well as the details
for the reaction of 4 and 6 with 1 are given in the Supporting
Information.
1-{2-[Bis(4-methoxyphenyl)phosphoryl]-3,4,5,6-tetraphenylphenyl}-
2-methoxynaphthalene (3d): Reaction of tetracyclone (1) and the
alkyne 2d according to the General Procedure gave the desired
compound 3d; yield 647 mg, 81 %; m.p. 278–279 °C. 1H NMR
(300 MHz, CDCl3): δ = 7.61 (d, J = 8.2 Hz, 1 H, Ar-H), 7.42 (d,
J = 7.6 Hz, 1 H, Ar-H), 7.35–7.26 (m, 2 H, Ar-H), 7.21–7.11 (m,
3 H, Ar-H), 7.06 (d, J = 9.0 Hz, 1 H, Ar-H), 6.89–6.54 (m, 16 H,
Ar-H), 6.48–6.37 (m, 5 H, Ar-H), 6.33 (d, J = 9.1 Hz, 1 H, Ar-H),
6.22–6.03 (m, 4 H, Ar-H), 3.68 (s, 3 H, OCH3), 3.61 (s, 3 H, Ar-
OCH3), 3.51 (s, 3 H, ArOCH3) ppm. 13C NMR (75 MHz, CDCl3):
δ = 160.9, 160.3, 153.1, 147.0, 145.0, 143.0, 142.5, 140.2, 139.6,
138.8, 134.8, 133.9, 132.6, 132.0, 131.4, 130.9, 129.7, 128.2, 127.2,
126.3, 125.4, 123.0, 122.4, 113.0, 112.2, 111.0, 60.4, 55.2, 55.1,
54.7 ppm. 31P NMR (125 MHz, CDCl3): δ = 25.7 ppm. MS
(70 eV): m/z (%) = 799 (92) [M+], 784 (37), 768 (29), 536 (100),
383 (29), 261 (68). C55H43O4P·(C4H8O2, EtOAc) (887.01): calcd. C
79.89, H 5.80; found C 79.94, H 5.95.
General Procedure for the Cycloaddition Reaction of Tetracyclone
(1) with Internal Alkynes 2a–l Yielding the Functionalized Biaryls
3: Acetylenes 2a–i (1 mmol), tetracyclone (384 mg, 1 mmol), and
diphenyl ether (2 g) were mixed in a Schlenk tube under argon, and
the flask was placed in a silicon oil bath at 260 °C for 8 h. After
cooling, the mixture was poured into n-hexane (30 mL), and pre-
cipitated products 3a–i were filtered off and washed with n-hexane.
They can be additionally purified by chromatography or recrystalli-
zation from ethyl acetate/n-hexane for extra purity.
1-[2-(Diphenylphosphoryl)-3,4,5,6-tetraphenylphenyl]naphthalene (3a):
Reaction of tetracyclone (1) and the alkyne 2a according to the
General Procedure gave the desired compound 3a; yield 652 mg,
1
92%; m.p. 286–287 °C. H NMR (300 MHz, CDCl3): δ = 7.96 (d,
J = 8.7 Hz, 1 H, Ar-H), 7.91 (d, J = 7.2 Hz, 1 H, Ar-H), 7.67 (d,
J = 7.8 Hz, 1 H, Ar-H), 7.54–7.29 (m, 11 H, Ar-H), 7.23–7.09 (m,
6 H, Ar-H), 7.02–6.89 (m, 6 H, Ar-H), 6.83–6.56 (m, 11 H, Ar-H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 147.6, 147.5, 145.4, 144.1,
144.0, 143.6, 143.5, 142.8, 142.7, 140.3, 140.0, 139.3, 138.9, 137.6,
137.5, 136.6, 135.0, 134.3, 134.0, 133.8, 133.2, 133.0, 132.2, 132.0,
131.9, 131.4, 131.3, 131.2, 130.6, 130.4, 130.3, 130.2, 130.1, 130.0,
129.0, 128.6, 128.5, 127.8, 127.7, 127.6, 127.1, 127.0, 126.7, 126.6,
126.3, 126.1, 126.0, 125.8, 125.6, 125.3, 125.0, 124.5 ppm. 31P
NMR (125 MHz, CDCl3): δ = 23.7 ppm. MS (70 eV): m/z (%) =
708 (100) [M+], 631 (18), 506 (27), 354 (11), 315 (15). C52H37OP
(708.82): calcd. C 88.11, H 5.26; found C 88.05, H 5.22.
1-[2-(Diphenylphosphoryl)-3,4,5,6-tetraphenylphenyl]-2-methylnaph-
thalene (3e): The reaction of tetracyclone (1, 0.5 mmol) and the
alkyne 2e (0.5 mmol) under the conditions described in the General
Procedure gave the desired compound 3e; yield 289 mg, 80%; m.p.
271–274 °C. 1H NMR (300 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz,
1 H, Ar-H), 7.54–7.41 (m, 2 H, Ar-H), 7.35–7.18 (m, 4 H, Ar-H),
7.10–6.90 (m, 9 H, Ar-H), 6.89–6.46 (m, 17 H, Ar-H), 6.41–6.31
(m, 3 H, Ar-H), 2.53 (s, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 147.4, 147.2, 145.8, 145.7, 143.5, 143.2, 142.0, 141.9,
141.8, 139.9, 139.7, 138.8, 138.1, 138.0, 135.6, 135.5, 135.3, 135.2,
134.5, 134.0, 133.6, 133.5, 133.1, 132.9, 132.3, 131.2, 131.1, 130.8,
130.5, 130.1, 130.0, 129.9, 129.7, 129.6, 129.0, 128.8, 128.7, 128.4,
127.9, 127.5, 127.4, 127.3, 127.2, 126.6, 126.4, 126.3, 126.2, 126.1,
125.9, 125.7, 125.5, 125.4, 125.3, 125.2, 124.2, 31.7, 22.7, 22.2 ppm.
31P NMR (125 MHz, CDCl3): δ = 24.1 ppm. MS (70 eV): m/z (%)
= 722 (32) [M+], 631 (100), 520 (45), 443 (16), 361 (12). C53H39OP
(722.85): calcd. C 88.06, H 5.44; found C 88.11, H 5.65.
1-[2-(Diphenylphosphoryl)-3,4,5,6-tetraphenylphenyl]-2-methoxy-
naphthalene (3b): After reaction of tetracyclone (1) and the alkyne
2b according to the General Procedure the desired compound 3b
was obtained; yield 613 mg, 83 %; m.p. 285–286 °C. 1H NMR
(300 MHz, CDCl3): δ = 8.03 (d, J = 8.4 Hz, 1 H, Ar-H), 7.84 (d,
J = 7.6 Hz, 1 H, Ar-H), 7.70 (d, J = 7.7 Hz, 2 H, Ar-H), 7.63–7.51
(m, 3 H, Ar-H), 7.40 (d, J = 9.7 Hz, 1 H, Ar-H), 7.36–7.05 (m, 12
1-[2-(Diphenylphosphanyl)-3,4,5,6-tetraphenylphenyl]-2-methoxy-
H, Ar-H), 7.01–6.95 (m, 10 H, Ar-H), 6.82 (d, J = 7.3, 1.3 Hz, 1 naphthalene (3f): According to the General Procedure tetracyclone
H, Ar-H), 6.76–6.65 (m, 2 H, Ar-H), 6.61–6.49 (m, 3 H, Ar-H), (1) and the alkyne 2f were reacted to give compound 3f; yield
3.99 (s, 3 H, OCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 171.6,
153.5, 147.4, 147.3, 145.6, 143.4, 143.3, 143.0, 142.9, 140.5, 140.3,
139.9, 139.7, 139.6, 138.7, 138.6, 137.3, 136.3, 136.2, 136.1, 135.0,
134.4, 134.3, 133.3, 133.2, 131.8, 131.5, 131.2, 131.0, 130.9, 130.6,
130.5, 130.0, 129.9, 129.7, 128.4, 127.6, 127.5, 127.0, 126.9, 126.8,
126.7, 126.6, 126.4, 126.0, 125.8, 125.7, 125.6, 123.4, 122.4, 117.1,
111.1, 60.9, 54.9 ppm. 31P NMR (125 MHz, CDCl3): δ = 24.1 ppm.
173 mg, 24 %; m.p. 220–221 °C (dec.). 1H NMR (300 MHz,
CDCl3): δ = 7.81 (d, J = 8.4 Hz, 1 H, Ar-H), 7.61–7.46 (m, 3 H,
Ar-H), 7.38–6.25 (m, 32 H, Ar-H), 3.66 (s, 3 H, OCH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 154.3, 154.2, 147.3, 143.6, 143.2,
143.1, 142.8, 142.2, 142.0, 140.6, 140.5, 140.4, 139.6, 137.5, 137.4,
137.3, 134.4, 134.2, 134.1, 132.7, 132.4, 132.3, 132.1, 131.4, 131.3,
131.0, 129.6, 129.5, 129.0, 128.0, 127.8, 127.4, 127.3, 127.0, 126.9,
MS (70 eV): m/z (%) = 738 (100) [M+], 536 (55), 353 (25), 201 (56). 126.6, 126.5, 126.4, 126.3, 126.2, 126.1, 125.9, 125.8, 125.7, 125.3,
C53H39O2P (738.85): calcd. C 86.16, H 5.32; found C 86.11, H 5.44.
125.2, 125.1, 124.9, 124.5, 124.4, 122.8, 111.4, 54.8 ppm. 31P NMR
512
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Eur. J. Org. Chem. 2010, 509–514