Aqueous Asymmetric Mukaiyama Aldol Reaction Catalyzed by Chiral Gallium Lewis Acid with Trost-Type Semi-Crown Ligands

Study of the lanthanide-catalyzed, aqueous, asymmetric Mukaiyama aldol reaction.

The development of efficient methods for the asymmetric Mukaiyama aldol reaction in aqueous solution has received great attention. We have developed a new series of chiral lanthanide-containing complexes that produce Mukaiyama aldol products with outstanding enantioselectivities. In this paper, we describe an optimized ligand synthesis, trends in stereoselectivity that result from changing lant...

Non-traditional hydrogen bond explanation of asymmetric catalysis of Mukaiyama aldol reactions by dinuclear zinc semi-crown ligands

Chemoselective silyl transfer in the Mukaiyama aldol reaction promoted by super silyl Lewis acid.

In the silyl Lewis acid-promoted Mukaiyama aldol reaction, the steric and electronic properties of the silyl group on the silyl Lewis acid influence the reaction mechanism and product distribution. When super silyl triflates such as (TMS)3SiOTf and (TES)3SiOTf are used as Lewis acids, the silyl group of the silyl enol ether chemoselectively transfers to the product. The mechanistic details have...

A new class of ligands for aqueous, lanthanide-catalyzed, enantioselective Mukaiyama aldol reactions.

The development of aqueous methods for generating enantiopure β-hydroxy carbonyl compounds is an important goal because these subunits compose many bioactive compounds and the ability to synthesize these groups in water has environmental and cost benefits. In this communication, we report a new class of ligands for aqueous, lanthanide-catalyzed, asymmetric Mukaiyama aldol reactions for the synt...

Disulfonimide-catalyzed asymmetric vinylogous and bisvinylogous Mukaiyama aldol reactions.

The term vinylogy, which describes a unique property of p systems where the electron density and reactivity is amplified along conjugated bonds, was proposed 75 years ago by Fuson. The principle becomes particularly relevant in the context of the aldol reaction: While metal dienolates often furnish mixtures of aand g-addition products, the corresponding dienolsilanes react with high selectivity...