Organometallics
Article
Preparation of 1-(3-Methoxy-6-phenylphenyl)-2,2-dimethyl-
1-propanone (10da). Acylaniline 2d (269 mg, 1.3 mmol), phenyl-
boronate (9a) (760 mg, 4.0 mmol), complex 1 (360 mg, 0.39 mmol),
and toluene (2 mL) were charged in a 10 mL Schlenk tube, and the
mixture was heated at 120 °C for 20 h. The reaction mixture was cooled
to room temperature and passed through a basic aluminum oxide
column (10:1 hexane/EtOAc). Silica gel column chromatography (30:1
hexane/EtOAc) of the resulting material afforded biaryl 10da as a brown
oil (178 mg, 51%). IR (KBr): 2967 m, 1688 s, 1605 m, 1565 w, 1479 s,
1410 w, 1364 w, 1309 m, 1289 s, 1232 s, 1168 m, 1052 m, 1034 m, 1007
w, 984 m, 856 m, 768 m, 736 w, 704 m, 575 w, 528 w cm−1. 1H NMR
(CDCl3): δ 0.87 (s, 9H, C(CH3)3), 3.84 (s, 3H, OCH3), 6.66 (d, J = 2.69
Hz, 1H, ArH), 6.97 (dd, J = 8.52, 2.69 Hz, 1H, ArH), 7.63−7.38 (m, 6H,
ArH). 13C NMR (CDCl3): δ 27.2, 44.9, 55.4, 111.3, 114.1, 127.2, 128.4,
129.5, 130.6, 131.0, 140.6, 142.0, 158.3, 216.3. HRMS (ESI) calcd for
[M + Na]+ (C18H20NaO2) m/z 291.1361. Found 291.1360.
Preparation of 1-{6-Phenyl-3-(trifluoromethyl)phenyl}-2,2-
dimethyl-1-propanone (10fa). Acylaniline 2f (490 mg, 2.0 mmol),
phenylboronate (9a) (760 mg, 4.0 mmol), complex 1 (370 mg, 4.0
mmol), and toluene (2 mL) were charged in a 10 mL Schlenk tube, and
the mixture was heated at 120 °C for 20 h. The reaction mixture was
cooled to room temperature and passed through a basic aluminum oxide
column (10:1 hexane/EtOAc). Silica gel column chromatography
(200:1 hexane/EtOAc) of the resulting material afforded biaryl 10fa as a
colorless oil (123 mg, 20%). IR (NaCl): 3365w, 3063 w, 3031 w, 2970
m, 2906 m, 2871 m, 1695 s, 1615 m, 1568 w, 1479 m, 1463 m, 1447 m,
1393 m, 1366 m, 1334 s, 1271 s, 1169 s, 1128 s, 1084 s, 1038 w, 1010 w,
982 m, 901 m, 841 m, 801 w, 777 m, 744 m, 726 m, 702 s, 655 m, 642 w,
596 w, 541 w, 517 w, 441 w, 427 w cm−1. 1H NMR (CDCl3): δ 0.87 (s,
9H, C(CH3)3), 7.31−7.42 (m, 6H, ArH), 7.52 (d, J = 8.1 Hz, 1H, ArH),
7.70 (d, J = 8.1 Hz, 1H, ArH); 13C NMR (CDCl3): δ 27.1, 45.1, 122.8 (q,
J = 3.8 Hz), 123.8 (q, J = 272 Hz), 125.5 (q, J = 3.8 Hz), 128.4, 128.9,
129.1 (q, J = 32 Hz), 130.3, 133.8, 139.5, 141.4, 141.6, 215.1. HRMS
(ESI) calcd for [M + Na]+ (C18H17F3NaO) m/z 329.1129. Found
329.1132.
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ASSOCIATED CONTENT
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* Supporting Information
1H and 13C{1H} NMR spectra of new compounds. This material
AUTHOR INFORMATION
Corresponding Author
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Notes
(14) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. Organometallics
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The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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This work was partially supported by the Grants-in-Aid for
Scientific Research from the Japan Society for the Promotion of
Science and the Ministry of Education, Culture, Sports, Science,
and Technology (MEXT) of Japan, by JST, ACT-C, and by the
Asahi Glass Foundation. T. Koreeda acknowledges a Research
Fellowship of JSPS for Young Scientists (5293).
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dx.doi.org/10.1021/om3011855 | Organometallics 2013, 32, 682−690