Rhodium‐ and Palladium‐Catalyzed Asymmetric Conjugate Additions

Conjugate Additions

“…The higher efficiency of this catalyst was also observed with other enone substrates and boronic acid derivatives (see Figure 5.1) [13,14]. It turned out that the acac ligand retards the transmetallation step owing to the high stability of the rhodium-acac moiety.…”

Enantioselective and Regiodivergent Copper-Catalyzed Electrophilic Arylation of Allylic Amides with Diaryliodonium Salts

“…Particularly appealing about the enantioselective arylation to form the β,β′diaryl enamides is their hydrolysis to the corresponding aldehyde; enantioenriched β,β′-diaryl aldehydes are useful building blocks that have a range of potential applications. 13 Acidic hydrolysis of enamide 5i was performed in 84% yield. The resulting aldehyde 6 could be converted into indatraline 7 , a nonselective monoamine transporter inhibitor that has shown promise in the treatment of cocaine addition (Scheme 3 ).…”

Ligand-accelerated enantioselective methylene C(sp 3 )–H bond activation

“…When considering retrosynthetic disconnections for the asymmetric synthesis of β-functionalized chiral carboxylic acids or amides, one immediately considers α,β-unsaturated esters or amides as building blocks which can be transformed to the desired products in the forward sense using state of the art conjugate addition reactions. Notably, Rh(I)-catalyzed asymmetric conjugate addition of α,β-unsaturated ketones with aryl boronic acids has afforded an elegant method for the preparation of chiral β-arylated compounds (17, 18). We therefore envision that enantioselective arylation of methylene C–H bonds at the β-position of amides through Pd(II) insertion could provide an alternative disconnection to these highly valuable synthons starting from saturated aliphatic acids (Fig.…”