Highly Recyclable Chemo‐/Biocatalyzed Cascade Reactions with Ionic Liquids: One‐Pot Synthesis of Chiral Biaryl Alcohols

Abstract

Distinct differentiation: β,β‐Disubstituted acrylic acids with sterically similar geminal diaryl groups can be hydrogenated with excellent enantioselectivities in the presence of a RhI complex formed in situ with two‐component ligands, a chiral secondary phosphine oxide (SPO) and an achiral phosphine (Ph3P). The sense of asymmetric induction was found to be controlled by the substrate configuration, thus allowing access to both enantiomers of the product with the same catalyst.

Combination of a Suzuki cross-coupling reaction using a water-soluble palladium catalyst with an asymmetric enzymatic reduction towards a one-pot process in aqueous medium at room temperature

“…Furthermore, exciting developments and improvements of this type of chemoenzymatic one-pot process for the synthesis of chiral biarylcontaining alcohols have been reported by other groups [4,7]. Cacchi et al demonstrated the suitability of palladium nanoparticles stabilised with DNA-binding protein (Pd np /Te-DPS) as a catalyst for the (phosphine-free) palladium-catalyzed Suzuki crosscoupling reaction step in this one-pot process [4].…”

“…Additionally and (important from a biocatalytic perspective) water enables as the "solvent of nature" the use of all types of enzymes. In this connection there has been a recent interest by various groups in the efficient combination of the Suzuki cross-coupling reaction as an example for a palladium-catalyzed synthesis with an asymmetric enzymatic reduction towards a chemoenzymatic one-pot process in aqueous reaction media [4,6,7]. The enzymatic reduction has been carried out under substrate-coupled cofactor regeneration [8,9] with isopropanol as reducing agent.…”

An imidazolium-based organopalladium-functionalized organic–inorganic hybrid silica promotes one-pot tandem Suzuki cross coupling–reduction of haloacetophenones and arylboronic acids

“…On the basis of the obtained heterogeneous catalyst 3, the Suzuki cross-coupling of 4-iodoacetophenone and phenylboronic acid to 1-(biphenyl-4-yl) ethanone, followed by the reduction of 1-(biphenyl-4-yl) ethanone to 1-(biphenyl-4-yl) ethanol were investigated at first [18][19][33][34][35][36][33][34][35][36][37][38][39]. According to the reported method [18], several bases were screened based on the same reaction solvent and reaction temperature in the literature.…”

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

“…There are a few successful examples of coupling Pd-catalyzed Suzuki cross-coupling reactions and Heck reactions in tandem with alcohol dehydrogenase in an aqueous buffer by using either a biphasic system [57] or additive tagged Pd-nanoparticles [58,59]. Recently, Zhao and coworkers successfully combined Ru-catalyzed olefin metathesis with a P450-monooxygenase catalyzed oxidation in a biphasic system for the synthesis of various epoxides [60].…”