Enantioselective Suzuki-Miyaura coupling

Asymmetric induction is attained for selected Suzuki-Miyaura aryl-aryl couplings (eq 9). In this case, more electron-rich MAP with PCy2 group exhibits higher enantioselectivities (up to 87% ee) than its PPh2 counterpart (75% ee). ... 

Enantioselective synthesis of axially chiral biaryls include all approaches where the starting material is achiral and the chirality is induced by an influence of chiral catalyst or reagent. Among enantioselective reactions that have been successfully used in the synthesis of axially chiral biaryls are the Kharasch reaction [34-36], Suzuki-Miyaura reaction [37,38], oxidative phenolic coupling mediated by copper complexes... 

One distinguishes palladium(0)- and palladium(ll)-catalysed reactions. The most common palladium(O) transformations are the Mizoroki-Heck and the cross-coupling transformations such as the Suzuki-Miyaura, the Stille and the Sonogashira reactions, which allow the arylation or alkenylation of C=C double bonds, boronic acid derivates, stan-nanes and alkynes respectively [2]. Another important palladium(O) transformation is the nucleophilic substitution of usually allylic acetates or carbonates known as the Tsuji-Trost reaction [3]. The most versatile palladium(ll)-catalysed transformation is the Wacker oxidation, which is industrially used for the synthesis of acetaldehyde from ethylene [4]. It should be noted that many of these palladium-catalysed transformations can also be performed in an enantioselective way [5]. 

Stereoselective modes of Suzuki-Miyura coupling a and b diastereoselective, c enantioselective Scheme 5.5 Alternative variants of Suzuki-Miyaura reaction... 

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