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. 2013 Jul 8;52(28):7198-202.
doi: 10.1002/anie.201300102. Epub 2013 May 29.

The supersilyl group as a carboxylic acid protecting group: application to highly stereoselective aldol and Mannich reactions

Jiajing Tan  1 , Matsujiro Akakura, Hisashi Yamamoto
Affiliations

The supersilyl group as a carboxylic acid protecting group: application to highly stereoselective aldol and Mannich reactions

Jiajing Tan et al. Angew Chem Int Ed Engl. .

Abstract

“Super Power”: The application of the "supersilyl” group as carboxylic acid protecting group has been investigated. The unique properties of the “supersilyl” group enabled it to outperform typical carboxyl protecting groups, conferring extraordinary protection upon the carboxyl functionality. “Supersilyl” esters were also utilized for the first time as stable carboxylic acid synthetic equivalents in highly stereoselective aldol and Mannich reactions. The value of this methodology has been further described by the easy photo-deprotection protocol and its applications in rapid synthesis of polyketide subunits.

Keywords: Mannich reaction; aldol reactions; carboxy groups; photodeprotection; protecting groups.

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Figures

Figure 1
Figure 1
Dolastatin D and erythromycin A.
Figure 2
Figure 2
Calculated enolates configuration and proposed TS.
Scheme 1
Scheme 1
“Supersilyl” esters synthesis and 1,4 addition reaction.
Scheme 2
Scheme 2
Deprotection methods.
Scheme 3
Scheme 3
Rapid synthesis of polyketide subunits. [a] Determined by 1H NMR of the crude product. [b] Yields for the major diastereom er. dr cannot be determined by the 1H NMR analysis.
Scheme 4
Scheme 4
anti-Selective aldol and Mannich reaction of Esters.
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