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. 2014 Jun 6;16(11):2954-7.
doi: 10.1021/ol501093v. Epub 2014 May 19.

Streocontrolled construction of six vicinal stereogenic centers on spiropyrazolones via organocascade Michael/Michael/1,2-addition reactions

Pankaj Chauhan  1 , Suruchi Mahajan, Charles C J Loh, Gerhard Raabe, Dieter Enders
Affiliations

Streocontrolled construction of six vicinal stereogenic centers on spiropyrazolones via organocascade Michael/Michael/1,2-addition reactions

Pankaj Chauhan et al. Org Lett. .

Abstract

A highly stereoselective one-pot procedure for the synthesis of spiropyrazolone derivatives bearing six contiguous stereogenic centers including two tetrasubstituted carbons has been developed. Under sequential catalysis by two organocatalysts, a cinchona-derived aminosquaramide and DBU, a series of diversely functionalized spiropyrazolones are obtained in good yields (47-62%) and excellent stereoselectivities (up to >25:1 dr and 98-99% ee). The opposite enantiomers of the spiropyrazolones are also accessible by employing a pseudoenantiomeric aminosquaramide catalyst.

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Figures

Figure 1
Figure 1
Biologically active pyrazolone derivatives.
Scheme 1
Scheme 1. Catalytic Enantioselective Strategies for the Synthesis of Spiropyrazolone Derivatives
Scheme 2
Scheme 2. Asymmetric Synthesis of Spiropyrazolone with Three Contiguous Tetrasubstituted Stereocenters
Scheme 3
Scheme 3. Gram-Scale One-Pot Stereoselective Synthesis of Spiropyrazolone 4a
See this image and copyright information in PMC

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