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Synfacts 2019; 15(09): 1029
DOI: 10.1055/s-0039-1690546
Metals in Synthesis
© Georg Thieme Verlag Stuttgart · New York

The Rhodium-Catalyzed Asymmetric 1,4-Addition

Contributor(s):
Paul Knochel
,
Ferdinand H. Lutter
Takaya Y, Ogasawara M, Hayashi T. * Sakai M, Miyaura N. * Kyoto University and Hokkaido University, Sapporo, Japan
Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl- and Alkenylboronic Acids to Enones.

J. Am. Chem. Soc. 1998;
120: 5579-5580
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Further Information

Publication History

Publication Date:
20 August 2019 (online)

 
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Key words

rhodium catalysis - asymmetric catalysis - boronic acids

Significance

In 1998, Hayashi and Miyaura reported the first asymmetric 1,4-addition of aryl- or alkenylboronic acids to various α,β-unsaturated ketones. A combination of a rhodium(I) catalyst with ethylene ligands, (S)-BINAP as chiral ligand and high reaction temperatures provided the corresponding addition products in remarkably high yields and enantiomeric ratios.


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Comment

This method provides numerous synthetic advantages, such as a high functional group tolerance of the organoboron reagent and aqueous reaction conditions, leading to products in very high enantiomeric ratios, which makes it the method of choice for the synthesis of these scaffolds. Thus, the scope for the reaction was further developed by using other Michael systems, such as α,β-unsaturated amides, phosphonates, and nitroalkenes (see Review below).


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Review

T. Hayashi, K. Yamasaki Chem. Rev. 2003, 103, 2829–2844.


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