2292
H. M. Hügel et al.
LETTER
OH–
2+
Ar-B(OH)2
Cu(OAc)2
O
oxidation
O2/OAc–
HN
AcO-B(OH)2
NH
O
1+
O
HOAc
Cu-OAc
O
Ar-N
NH
2+
AcO-Cu-N
reductive
elimination
O
2+
NH
Ar-Cu-OAc
O
3+
Ar Cu OAc
Ar-B(OH)2
O
N
O
NH
O
AcO-B(OH)2
HN
oxidation
O
NH
2+
OH–
O
Ar-Cu-N
NH
O2/OAc–
HOAc
O
Scheme 4 Copper(II)-promoted N-arylation of 5,5-dimethylhydantoin
(16) Battmann, T.; Bonfils, A.; Branche, C.; Humbert, J.;
Goubert, F.; Teutsch, G.; Philibert, D. J. Steroid Biochem.
Mol. Biol. 1994, 48, 55.
References and Notes
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391.
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Chemistry for Organic Synthesis, Vol. I; Negishi, E.-I.; de
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M.; Lumpkin, C. C. J. Am. Chem. Soc. 1953, 75, 2708.
(b) Kang, S.-K.; Lee, S.-H.; Lee, D. Synlett 2000, 1022.
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Vincent, G.; Clark, C. G.; Deudon, S.; Yadhav, P. K.
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(23) General Procedure: Imide (2.1 mmol), Cu(OAc)2 (2.0
mmol, 0.38 g), 4 Å molecular sieves (750 mg crushed in a
mortar) and triarylbismuthane or arylboronic acid (2.5
mmol) were combined in a Schlenk flask (100 mL) and
anhyd CH2Cl2 (50 mL) and pyridine (0.2 mL) were added.
The flask was flushed with pure oxygen for 5 min, sealed
(glass stopper tightened with Teflon ring) and the reaction
mixture stirred for 7 d (TLC monitor) during which time the
blue colour of the Cu(OAc)2 turned green. The solution was
filtered through celite and thoroughly extracted with CH2Cl2
(3 × 50 mL) and EtOAc (3 × 50 mL). The solvent was re-
moved in vacuo. The residue was mixed with, and impreg-
nated on, silica gel, and then separated via flash column
chromatography (hexane–EtOAc; 4:1 for phthalimide deri-
vatives; 2:3 for succinimide and 5,5¢-dimethylhydantoin
derivatives).
(15) Yee, N. K. Org. Lett. 2000, 2, 2781.
Synlett 2006, No. 14, 2290–2292 © Thieme Stuttgart · New York