Harald Gröger

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic Enantioselective Strecker Reactions and Analogous SynthesesHarald GrögerView Author Information Degussa AG, Project House Biotechnology, Rodenbacher Chaussee 4, 63457 Hanau-Wolfgang, Germany Cite this: Chem. Rev. 2003, 103, 8, 2795–2828Publication Date (Web):July 26, 2003Publication History Received22 January 2003Published online26 July 2003Published inissue 1 August 2003https://pubs.acs.org/doi/10.1021/cr020038phttps://doi.org/10.1021/cr0200

Can a simple amino acid act like an enzyme? This question is reviewed and discussed herein. In addition, new contributions in which simple organic molecules are used as efficient chiral catalysts in asymmetric synthesis (see scheme) are highlighted.

New and highly efficient methods based on various catalytic concepts have recently been developed for the asymmetric aldol reaction. These include new transition metal based catalysts, creative approaches for activating the ketone, and the use of novel chiral nonmetallic Lewis acids and Lewis bases as catalysts, shown schematically on the right.

An important class of compounds which can be produced by means of enzymatic routes are enantiomerically pure aromatic α-hydroxy carboxylic acids, in particular mandelic acid and derivatives thereof. Numerous different types of enantioselective biocatalytic approaches to these target molecules have been developed. Among them are chiral enzymatic resolution processes using racemic precursors as well as asymmetric catalytic methods starting from prochiral compounds. Regarding the resolution process

Innovative and highly efficient catalytic methods for the enantioselective preparation of biologically active α-amino phosphonates and α-hydroxy phosphonates have recently been developed. These asymmetric catalytic reactions are based on different concepts, namely hydrogenation, reduction, dihydroxylation, aminohydroxylation, and hydrophosphonylation processes. The enantioselective synthesis of α-amino- and α-hydroxy phosphonates by catalytic processes has attracted considerable interest in the

Bifunctional catalysts can drastically improve the efficiency of asymmetric processes with respect to enantioselectivity and/or conversion rate. A new type of chiral bifunctional catalyst has been developed recently in the Shibasaki group that contains both Lewis acid and Lewis base moieties. These monometallic and bifunctional phosphinoyl-containing catalysts are able to coordinate both nucleophilic and electrophilic substrates in the transition state. Several successful applications of this ne

The catalytic and enantioselective hydrophosphonylation of cyclic imines is described for the first time. In addition, we have uncovered a new and highly efficient asymmetric approach to cyclic α-amino phosphonates using thiazolines as the imine model component. The desired pharmaceutically interesting phosphonates 5a−e could be synthesized by a heterobimetallic (R)-LnPB-catalyzed (Ln = lanthanoid metal, P = potassium, B = (R)=binaphthol) hydrophosphonylation of the CN double bond with up to 98%

Productive cells: In a simple, highly efficient process for the synthesis of optically active alcohols, ketones are reduced by “designer cells” at high substrate concentrations and without the addition of an “external” cofactor in aqueous reaction medium. A wide range of R and S alcohols can be prepared with conversions of >90 % and enantioselectivities of >99 % ee (scheme shows results from the application on a 10-L scale). Supporting information for this article is available on the WWW under h

The enantioselective synthesis of alpha-amino- and alpha-hydroxy phosphonates by catalytic processes has attracted considerable interest in the last few years, not least because of the pharmaceutical interest in such compounds. This article contains a compilation of the asymmetric synthesis methods developed to date. The described synthetic routes are based on different catalytic concepts, namely, hydrogenation, reductions, dihydroxylation, aminohydroxylation, and hydrophosphonylation.

Chemoenzymatic catalysis, by definition, involves the merging of sequential reactions using both chemocatalysis and biocatalysis, typically in a single reaction vessel. A major challenge, the solution to which, however, is associated with numerous advantages, is to run such one-pot processes in water: the majority of enzyme-catalyzed processes take place in water as Nature's reaction medium, thus enabling a broad synthetic diversity when using water due to the option to use virtually all types o

A Wacker oxidation using CuCl/PdCl2 as a catalyst system was successfully combined with an enzymatic ketone reduction to convert styrene enantioselectively into 1-phenylethanol in a one-pot process, although the two reactions conducted in aqueous media are not compatible due to enzyme deactivation by Cu ions. The one-pot feasibility was achieved via compartmentalization of the reactions. Conducting the Wacker oxidation in the interior of a polydimethylsiloxane thimble enables diffusion of only t

The catalyst loading in the narrow range between 0.5 and 10 mol % determines whether an enantioselective organocatalytic aldol reaction proceeds under kinetic or thermodynamic control; high conversions and ee values can be achieved with low catalyst loadings (see scheme). Since the reaction is carried out in water, it can be combined with a biocatalytic reduction for the one-pot synthesis of 1,3-diols with d.r. >25:1 and 99 % ee. Detailed facts of importance to specialist readers are published a