Nonenzymatic enantioselective synthesis of all-carbon quaternary centers through desymmetrization

Abstract

The asymmetric desymmetrization of meso or prochiral compounds containing an all-carbon quaternary center is an attractive alternative to classical synthetic approaches aimed at the asymmetric formation of a new C—C bond. This review focuses on nonenzymatic desymmetrizations that utilize transition metal catalysts or organocatalysts to distinguish between enantiotopic groups to generate enantioenriched compounds containing all-carbon quaternary stereocenters.

Rhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers

“…7 Herein, we disclose a desymmetrization of bisallylaldehydes 1 to generate cyclohexenes 4 via the desymmetrization of prochiral quaternary centers (Figure 1c-route A). 7–10 Our Rh-catalyzed method provides enantioselective access to the 3,5,5-trisubstituted cyclohexene motif that is inaccessible by the well-established Diels–Alder reaction and therefore complements conventional cycloadditions (Figure 1d). 11 …”

Non-Enzymatic Desymmetrization Reactions in Aqueous Media

“…A fairly good number of reviews of enzymatic desymmetrization reactions have already been published [1][2][3][4][5][6][7][8][9], and reviews of non-enzymatic desymmetrization reactions in organic solvents have also been published [10][11][12][13]. Therefore, this review highlights some of the recent progress in the research of non-enzymatic desymmetrization reactions in A fairly good number of reviews of enzymatic desymmetrization reactions have already been published [1][2][3][4][5][6][7][8][9], and reviews of non-enzymatic desymmetrization reactions in organic solvents have also been published [10][11][12][13]. Therefore, this review highlights some of the recent progress in the research of non-enzymatic desymmetrization reactions in aqueous reaction media.…”

Organocatalytic enantioselective desymmetrisation

“…With the appropriate choice of reagents and catalysts, multiple stereocentres can be set in one reaction with high enantioselectivity, making such strategies especially attractive in complex natural product synthesis. [3][4][5][6][7][8][9][10][11] This review seeks to provide an overview of recent developments (since 2010) of organocatalytic enantioselective desymmetrisations. In particular, the advent of organocatalysis has opened up many exciting new opportunities, providing fundamentally different reactivity modes to more traditional metal-catalysed desymmetrisations.…”