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