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Synthesis 2011(14): 2175-2191  
DOI: 10.1055/s-0030-1260040
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Acetate Aldol Reactions from Metal Enolates

Xavier Ariza, Jordi Garcia, Pedro Romea*, Fèlix Urpí*
Departament de Química Orgànica, Universitat de Barcelona, Martí i Franqués 1-11, 08028 Barcelona, Catalonia, Spain
Fax: +34(93)3397878; e-Mail: pedro.romea@ub.edu; e-Mail: felix.urpi@ub.edu;
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Publication History

Received 27 January 2011
Publication Date:
10 May 2011 (online)

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Abstract

This review deals with stereoselective acetate aldol reactions mediated by metal enolates. It summarizes recent advances in aldol additions of unsubstituted metal enolates that either incorporate chiral auxiliaries, stoichiometric Lewis acids, or catalytic Lewis acids or bases, or act in substrate-controlled reactions. These approaches provide stereocontrolled aldol transformations that allow the efficient synthesis of structurally complex natural products.

1 Introduction

2 Chiral Auxiliaries

3 Stoichiometric Lewis Acids

4 Catalytic Lewis Acids and Bases

5 Substrate-Controlled Aldol Reactions

5.1 α-Methyl Ketones

5.2 α-Hydroxy Ketones

5.3 β-Hydroxy Ketones

5.4 β-Hydroxy α-Methyl Ketones

5.5 α,β-Dihydroxy Ketones

5.6 Remote Stereocontrol

6 Conclusions

Key words

stereoselective acetate aldol reactions - metal enolates - chiral auxiliaries - Lewis acids - substrate-controlled reactions

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4

The term acetate aldol reaction refers to any aldol transformation involving unsubstituted enolates, which encompasses the reactions of acetate esters, other carboxylic derivatives, and methyl ketones.

8

The term metal enolate is used in a broad sense. It refers to enolates from boron, silicon, alkaline, titanium, tin, and other elements that participate in aldol reactions proceeding through cyclic transition states

10

Stereoselective aldol reactions involving multifunctional catalysts often proceed through highly organized transition states that have more complex molecular arrangements

15

It is worth recalling that the N-propanoyl counterpart was absolutely successful under the same experimental conditions and provided the Evans-syn diastereomer with a dr of 99.4:0.6. See reference 5a.

19

Oxazolidinethiones turned out to be slightly less stereo-selective than the corresponding thiazolidinethiones for α,β-unsaturated aldehydes.

23

Boron enolates afforded lower diastereomeric ratios.

67

Similar results are obtained with other aliphatic α,β-unsaturated and aromatic aldehydes.

71

In support of this theoretical model, it has been observed that the more sterically bulky the R group (Me to i-Pr), the better the diastereoselectivity for aliphatic as well as α,β-unsat-urated and aromatic aldehydes.

92

See reference 81l and 82a.