C
J. Tang et al.
Cluster
Synlett
diphenylated benzaldehyde 3p. C4-substituted biphenyl-2-
carbaldehydes 3q–s were also obtained by this method,
albeit in low conversions.
Note that the chromium-catalyzed, one-pot coupling
reaction of C–O bond with bromobenzene is scalable and
can be performed on a one gram scale without loss of effi-
ciency (Scheme 4). The application of this protocol in the
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synthesis of functionalized fluorenone compound
4
through an intramolecular cyclization was also successful.23
1) CrCl2 (10 mol%)
Mg (2.2 equiv)
THF, r.t., 12 h
H
NtBu
OMe
H
O
Ph
Br
+
2) HCl (aq), 0.5 h
Ph
3b
2b
1a
(1.5 g, 7.8 mmol)
(1.43 g, 71%)
O
TEAB
(10 mol%)
K2S2O8 (2 equiv)
DCE, 120 °C, 36 h
Ph
4 (66%)
Scheme 4 Gram scale synthesis and cyclization of product 3b
In summary, we have developed an operationally sim-
ple, one-pot coupling reaction of C–O bonds with organic
bromides by chromium catalysis. The addition of metallic
magnesium into the reaction system is essential to ensure
that the cross-coupling proceeds smoothly at room tem-
perature. This methodology has a synthetic advantage over
the previous one using organomagnesium reagents that
were made separately from halide electrophiles before the
cross-coupling. Further studies in developing new coupling
models with chromium catalysis is ongoing in our laboratory.
Funding Information
We thank the National Natural Science Foundation of China, SCU, and
Beijing National Laboratory for Molecular Sciences for financial sup-
port.
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Supporting information for this article is available online at
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References and Notes
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–D