Catalytic Enantioselective Desymmetrization of Meso Compounds in Total Synthesis of Natural Products: Towards an Economy of Chiral Reagents

In memory of our friend and colleague, Professor Teodor Silviu Balaban

Abstract

Meso compounds represent a particular family of achiral molecules bearing elements of chirality. Their desymmetrization through enantioselective catalytic methods usually leads to elaborate chiral building blocks containing several stereogenic elements, which can be a very useful and elegant approach in the context of total synthesis. In the present review, the power of this strategy is illustrated through the different possibilities of catalytic enantioselective desymmetrization. From the combination of the hidden symmetry detection and the catalytic enantioselective transformations a new type of economy emerges: the economy of chiral reagents.

1 Introduction

1.1 What Is a Meso Compound?

1.2 Why Is the Catalytic Enantioselective Desymmetrization of Meso Compounds a Powerful Strategy in Total Synthesis?

1.3 Toward an Economy of Chiral Reagents

2 Enzymatic Desymmetrization

2.1 (–)-Sceptrin (Baran, 2006)

2.2 cis-Solamin (Stark, 2006)

2.3 Crocacin C (2010, Bressy/Pons)

3 Metallocatalyzed Desymmetrization

3.1 Quadrigemine C (2002, Overman)

3.2 (+)-Homochelidonine (2007, Lautens)

3.3 (–)-Cyanthiwigin F (2008, Stoltz)

3.4 [5]-Ladderanoic Acid (2016, Gonzalez-Martinez/Boxer/Burns)

4 Organocatalyzed Desymmetrization

4.1 (+)-Hirsutene (2008, List)

4.2 Alstoscholarines (2011, Neuville/Zhu)

4.3 (–)-Diospongin A (2015, Chuzel/Bressy)

5 Conclusion

Key words

total synthesis - natural product - meso compounds - desymmetrization - enantioselective catalysis - economy of chiral reagents - hidden symmetry - amplification

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