Chiral lanthanoid complexes, asymmetric catalysis

Catalysis, Asymmetric, with Chiral Lanthanoid Complexes (Shibasaki and... 

Shibasaki M., Sasai H. Asymmetric Catalysis With Chiral Lanthanoid Complexes... 

Shibasaki, M., Asymmetric Catalysis with Chiral Lanthanoid Complexes, 22, 201. 

IV. Previous examples of asymmetric catalysis with chiral lanthanoid complexes... 

The third part of this chapter reviews previously described catalytic asymmetric reactions that can be promoted by chiral lanthanoid complexes. Transformations such as Diels-Alder reactions, Mukaiyama aldol reactions, several types of reductions, Michael addition reactions, hydrosilylations, and hydroaminations proceed under asymmetric catalysis in the presence of chiral lanthanoid complexes. 

IV. PREVIOUS EXAMPLES OF ASYMMETRIC CATALYSIS WITH CHIRAL LANTHANOID COMPLEXES... 

As discussed in Section III J, in general, catalytic asymmetric aldol reactions have been studied using enol silyl ethers, enol methyl ethers, or ketene silyl acetals as a starting material. So far several types of chiral catalysis have been reported.75-85 The chiral lanthanoid complex prepared from Ln(OTf)3 and a chiral sulfonamide ligand was effective in promoting an asymmetric Mukaiyama aldol reaction with a ketene silyl acetal.86 The preparation of the catalyst and a representative reaction are shown in Figure 45. 

Chiral Lanthanoid Complexes, Asymmetric Catalysis with (Shibasaki and Sasai). .. 22 201... 

In 1992, Shibasaki et al. reported for the time an application of chiral heterobimetallic lanthanoid complexes (LnLB) as chiral catalysts in asymmetric catalysis, namely the catalytic asymmetric nitroaldol reaction (Henry reaction), which is one of the most classical C-C bond forming processes [11]. Additionally, this work represents the first enantioselective synthesis of (3-nitroalcohol compounds by the way of enantioselective addition of nitroalkanes to aldehydes in the presence of a chiral catalyst. The chiral BINOL based catalyst was prepared starting from anhydrous LaCl3 and an equimolar amount of the dialkali metal salt of BINOL in the presence of a small amount of water [9]. 

In this chapter, we reviewed recent developments regarding lithium, sodium, and potassium salt based-catalysis, with a particular focus on asymmetric catalysts. While these alkali-metal salts have traditionally been used as simple bases, recent advances based on chiral multifunctional acid-base combination chemistry, using chiral crown-alkali-metal complexes, chiral lanthanoid/alkali-metal complexes, chiral alkali-metal alkoxides, and chiral alkali-metal phosphates, have also been outstanding. These synergic acid-base catalyst systems should enable more efficient and/or new transformations that have not been possible thus far using conventional catalysts that only rely on Lewis acidity or Bronsted/Lewis basicity. 

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