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DOI: 10.1055/s-0028-1088118
New and Efficient Protocol for Arylation of Quinones
Publication History
Publication Date:
26 March 2009 (online)
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Abstract
A practical rhodium-mediated arylation of 1,4-quinones has been developed. The corresponding 2-aryl-1,4-quinones were obtained with excellent selectivity and high yields under convenient aerobic reaction conditions.
Key words
arylation - homogeneous catalysis - quinones - rhodium - cross-coupling
- 1
Chemistry of the Quinoid
Compounds
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References
Typical Coupling
Procedure: A glass vial was loaded with [Rh(cod)Cl]2 (5
mg, 0.01 mmol), Et(CO)Me (5 mL) and COD (35 µL, 0.2 mmol).
Then, 1 (137 mg, 1.5 mmol), 2b (264
mg, 1 mmol), and KHSO4 (137mg, 1 mmol) were sequentially
added with stirring. The vial was then equipped with a condenser
capped with a PP-cap and was put into a (95 ˚C)
hot oil bath to be stirred for 18 h. After that time, the reaction
mixture was allowed to cool down to r.t. Products 3 and 5 could be isolated by MPLC on this stage
or only 3 after oxidation.
Oxidation: NaIO4 (213 mg, 1
mmol) and Bu4NBr (80 mg, 0.25 mmol) were added to the
coupling reaction mixture and stirred at r.t. for 3 h. Bu4NIO4 (110
mg, 0.25 mmol) was then added. After 21 h of stirring at r.t. solvent
was evaporated off, and 3 was chromatographically
isolated (SiO2, 20-400 mesh; hexane-acetone,
6:1) to yield 3 (273 mg, 87%);
mp 121-123 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 3.90
(s, 3 H), 7.09 (s, 1 H), 7.37-7.40 (m, 2 H), 7.44 (t, J = 7.2 Hz,
1 H), 7.62 (d, J = 8.4
Hz, 1 H), 7.81-7.83 (m, 2 H), 7.86 (d, J = 8.4 Hz,
1 H), 7.98 (d, J = 9.2
Hz, 1 H), 8.19-8.23 (m, 2 H).
¹³C
NMR (100 MHz, CDCl3): δ = 56.6,
113.1, 116.9, 123.8, 123.9, 126.2, 127.1, 127.2, 128.4, 129.0, 131.1,
132.4, 132.5, 132.6, 133.7, 133.8, 139.3, 147.1, 154.4, 183.8, 185.1.
Anal. Calcd for C21H14O3: C, 80.24;
H, 4.49. Found: C, 79.75; H, 4.81.