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DOI: 10.1055/s-0033-1340439
Enantioselective Low-Temperature 1,4-Addition of Arylboronic Acids
Publication History
Publication Date:
13 December 2013 (online)
Key words
rhodium - asymmetric 1,4-addition - arylboronic acids - α,β-unsaturated carbonyls - low-temperature addition![](https://www.thieme-connect.de/media/synfacts/201401/i_h160_s1_10-1055_s-0033-1340439.gif)
Significance
Although various chiral rhodium catalysts have been developed, the rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds below 0 °C has not been achieved. This paper describes the rhodium-catalyzed enantioselective 1,4-addition of arylboronic acids at low temperature. The use of the highly electron-poor (R)-MeO-F12-BIPHEP ligand can retain the activity of the rhodium catalyst, which can serve to improve enantioselectivities.
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Comment
A variety of N-substituted maleimides are applicable to this method, affording the corresponding chiral succinimides in excellent yields and enantioselectivities. Notably, the enantioselective 1,4-addition to N-H-maleimide, which has been reported as an inactive substrate for rhodium-catalyzed asymmetric 1,4-addition, is also successful. When the reaction is performed at –50 °C, the enantioselectivity is improved to up to 87% ee.
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![](https://www.thieme-connect.de/media/synfacts/201401/i_h160_s1_10-1055_s-0033-1340439.gif)