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(0.62 mL, 5 mmol) to give the arylzinc derivative (3.95 mmol, 79 % 1444, 1302, 1248, 1126, 813 cm–1. C29H18O (382.46): calcd. C 91.07,
GC yield). Ethyl chloroformate (0.16 mL, 1.58 mmol) was then added H 4.74; found C 90.97, H 4.64.
to the arylzinc bromide mixture. Purification on silica gel (petroleum
Bis(5-fluoro-2-methylphenyl)methanone (1t): The preparation
followed general procedure B by using 2-bromo-4-fluorotoluene
(0.62 mL, 5 mmol) to give the arylzinc derivative (4.75 mmol, 95 %
GC yield). Ethyl chloroformate (0.19 mL, 1.9 mmol) was then added
ether/ethyl acetate, 10:1–7:1) afforded 1o (324 mg, 84 %yield) as a
white powder. 1H NMR (300 MHz, CDCl3): δ = 7.51 (dd, J = 7.6,
1.7 Hz, 2 H), 7.43 (td, J = 7.9, 1.7 Hz, 2 H), 6.98 (td, J = 7.6, 0.8 Hz,
2 H), 6.91 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
to the arylzinc bromide mixture. Purification on silica gel (petroleum
195.4, 158.4, 132.7, 130.5, 130.5, 120.4, 111.6, 55.8 ppm. HRMS (EI+):
ether/ethyl acetate, 25:1–20:1) afforded 1t (259 mg, 55 % yield) as
calcd. for C15H14O3 242.0943; found 242.0955.[27]
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a colorless liquid. H NMR (300 MHz, CDCl3): δ = 7.19 (dd, J = 8.5,
5.4 Hz, 2 H), 7.05 (td, J = 8.2, 2.8 Hz, 2 H), 6.95 (dd, J = 8.9, 2.8 Hz,
Diethyl 3,3′-Carbonyldibenzoate (1p): The preparation followed
general procedure B by using ethyl 3-bromobenzoate (0.80 mL,
2 H), 2.33 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 198.1, 160.6
(d, J = 245.7 Hz), 139.5 (d, J = 5.7 Hz), 133.9 (d, J = 3.5 Hz), 133.2
(d, J = 7.2 Hz), 118.4 (d, J = 7.2 Hz), 116.8 (d, J = 22.4 Hz), 17.0 ppm.
19F NMR [282 MHz, CDCl3, bis(trifluoromethane)sulfonimide as ex-
ternal reference]: δ = –116.70 ppm. HRMS (EI+): calcd. for C15H12F2O
5 mmol) to give the arylzinc derivative (4.2 mmol, 84 % GC yield).
Ethyl chloroformate (0.17 mL, 1.68 mmol) was then added the aryl-
zinc bromide mixture. Purification on silica gel (petroleum ether/
ethyl acetate, 15:1–12:1) afforded 1p (290 mg, 53 % yield) as a white
powder; m.p. 99.4 °C. 1H NMR (300 MHz, CDCl3): δ = 8.45 (dd, J =
1.5, 1.3 Hz, 2 H), 8.29 (ddd, J = 7.8, 1.5, 1.3 Hz, 2 H), 7.98 (ddd, J =
7.8, 1.5, 1.3 Hz, 2 H), 7.60 (t, J = 7.8 Hz, 2 H), 4.41 (q, J = 7.1 Hz, 4
H), 1.40 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
195.1, 165.8, 137.6, 134.1, 133.7, 131.2, 131.1, 128.8, 61.6, 14.5 ppm.
HRMS (EI+): calcd. for C19H18O5 326.1154; found 326.1151. FTIR
246.0856; found 246.0853. FTIR (KBr): ν = 2930, 1673, 1609, 1581,
˜
1489, 1405, 1305, 1260, 1235, 1171, 822 cm–1. C15H12F2O (246.26):
calcd. C 73.16, H 4.91; found C 73.00, H 4.99.
Di(furan-3-yl)methanone (1u): The preparation followed general
procedure B by using 3-bromofuran (0.25 mL, 2.78 mmol) to give
the arylzinc derivative (2.34 mmol, 84 % GC yield). Ethyl chloro-
formate (0.09 mL, 0.94 mmol) was then added to the arylzinc brom-
ide mixture. Purification on silica gel (petroleum ether/ethyl acetate,
(neat): ν = 2982, 1717, 1664, 1603, 1367, 1272, 1227, 1154, 1102,
˜
1080, 1022 cm–1. C19H18O5 (326.35): calcd. C 69.93, H 5.56; found C
69.79, H 5.50.
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15:1) afforded 1u (122 mg, 80 % yield) as a white powder. H NMR
(300 MHz, CDCl3): δ = 8.03 (t, J = 0.8 Hz, 2 H), 7.50 (t, J = 1.6 Hz, 2
H), 6.88 (dd, J = 1.6, 0.8 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 191.9, 147.0, 144.3, 127.8, 109.7 ppm. HRMS (EI+): calcd. for
C9H6O3 162.0317; found 162.0312.[28]
Bis(4-fluorophenyl)methanone (1q): (CAS: 345-92-36) The prepa-
ration followed general procedure B by using 1-bromo-4-fluoro-
benzene (0.55 mL,
5 mmol) to give the arylzinc derivative
(4.45 mmol, 89 % GC yield). Ethyl chloroformate (0.18 mL,
1.78 mmol) was then added to the arylzinc bromide mixture. Purifi-
cation on silica gel (petroleum ether/ethyl acetate, 15:1) afforded
1q (388 mg, >99 % yield) as a white powder. 1H NMR (300 MHz,
CDCl3): δ = 7.85–7.77 (m, 4 H), 7.21–7.11 (m, 4 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 193.9, 165.5 (d, J = 254.2 Hz), 133.9 (d, J =
3.1 Hz), 132.6 (d, J = 9.1 Hz), 115.7 (d, J = 21.9 Hz) ppm. 19F NMR
[282 MHz, CDCl3, bis(trifluoromethane)sulfonimide as external refer-
ence]: δ = –105.73 ppm. HRMS (EI+): calcd. for C13H8F2O 218.0543;
found 218.0539.[23]
Acknowledgments
The authors thank the French Ministère de l'Enseignement Su-
périeur et de la Recherche (Ph.D. grant to A. R.). This work was
supported by the Centre National de la Recherche Scientifique
(CNRS) and the Ecole Polytechnique, Paris.
Keywords: Synthetic methods · Homogeneous catalysis ·
Di-o-tolylmethanone (1r): (CAS: 1018-97-9) The preparation fol-
lowed general procedure B by using 2-bromotoluene (0.60 mL,
5 mmol) to give the arylzinc derivative (3.50 mmol, 70 % GC yield).
Ethyl chloroformate (0.14 mL, 1.4 mmol) was then added to the
arylzinc bromide mixture. Purification on silica gel (petroleum
ether/ethyl acetate, 25:1–20:1) afforded 1r (234 mg, 80 % yield) as
a white powder. 1H NMR (300 MHz, CDCl3): δ = 7.39 (td, J = 7.4,
1.4 Hz, 2 H), 7.31 (m, 4 H), 7.20 (t, J = 7.4 Hz, 2 H), 2.46 (s, 6 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 200.8, 139.1, 138.2, 131.5, 131.1, 130.4,
125.5, 20.7 ppm. HRMS (EI+): calcd. for C15H14O 210.1045; found
210.1039.[23]
Cross-coupling · Cobalt · Zinc
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Di(phenanthren-9-yl)methanone (1s): The preparation followed
general procedure B by using 9-bromophenanthrene (1.286 g,
5 mmol) to give the arylzinc derivative (3.3 mmol, 66 % GC yield).
Ethyl chloroformate (0.13 mL, 1.3 mmol) was then added to the
arylzinc bromide mixture. Purification on silica gel (petroleum
ether/ethyl acetate, 30:1) afforded 1s (185 mg, 37 % yield) as a
white powder; m.p. 194.5 °C. 1H NMR (300 MHz, CDCl3): δ = 8.81 (d,
J = 8.2 Hz, 2 H), 8.75 (d, J = 8.7 Hz, 2 H), 8.69 (dd, J = 8.2, 0.9 Hz, 2
H), 8.01 (s, 2 H), 7.82–7.73 (m, 6 H), 7.69 (td, J = 7.6, 1.2 Hz, 2 H),
7.59 (td, J = 7.5, 0.9 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
199.5, 136.3, 132.7, 132.1, 131.0, 130.2, 130.1, 129.6, 129.1, 127.8,
127.8, 127.5, 127.0, 126.1, 122.9 ppm. HRMS (EI+): calcd. for C29H18
O
382.1358; found 382.1357. FTIR (neat): ν = 3055, 1646, 1526, 1493,
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