Hayashi-Miyaura reaction chiral ligands

Liao and coworkers [49], in 2011, reported the synthesis of a new family of benzene-based chiral hetero-disulfoxide ligands and applied them successfully in the Rh-catalyzed asymmetric 1,4-addition of arylboronic adds to chromenones. The application of the Hayashi-Miyaura reaction on these substrate types is without a doubt a milestone in the development of this process, as the synthesis of enantiopure flavanones is a significantly challenging undertaking. With this procedure, the authors achieved the desired addition products in up to 70% yield and up to 95% ee (Scheme 5.12). 

Figure 5.17 Chiral hybrid sulfoxide-olefin ligands and their application in the Hayashi-Miyaura reaction...

Following the initial work by Hayashi and Miyaura using (5)-binap, several other chiral ligands were reported to achieve high enantioselectivity in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to ot,p-enones (Figure 3.18). A polymer-supported (X)-binap analog 42 was also synthesized and it was successfully utilized in the rhodium-catalyzed asymmetric 1,4-addition reactions in water (Figure 3.19)." The stereoselectivities observed in this system are comparable to those obtained in the unsupported Rh/(5)-binap system. It was also... 

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