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. 2011 Aug 22;50(35):8167-71.
doi: 10.1002/anie.201103470. Epub 2011 Jul 7.

Scaffolding catalysts: highly enantioselective desymmetrization reactions

Xixi Sun  1 , Amanda D Worthy, Kian L Tan
Affiliations

Scaffolding catalysts: highly enantioselective desymmetrization reactions

Xixi Sun et al. Angew Chem Int Ed Engl. .

Abstract

Ex-changing places: a highly enantioselective desymmetrization of 1,2-diols has been developed in which the catalyst utilizes reversible covalent bonding to the substrate to achieve both high selectivity and rate acceleration (see scheme, PMP=pentalmethylpiperidine, TBS=tert-butyldimethylsilyl). Induced intramolecularity is responsible for the enhanced rate, thus allowing the reaction to be performed at room temperature.

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Figures

Figure 1
Figure 1
Catalytic cycle for scaffolding catalysis
Figure 2
Figure 2
Catalyst design
Figure 3
Figure 3
Proposed catalytic cycle for silylation
Figure 4
Figure 4
X-ray structure of 6
Scheme 1
Scheme 1
Silylation with TESCl
Scheme 2
Scheme 2
Control reaction
Scheme 3
Scheme 3
Exchange of 4b with isopropanol and substrate
See this image and copyright information in PMC

References

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