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. 2011 Apr 20;133(15):5776-9.
doi: 10.1021/ja201321v. Epub 2011 Mar 30.

Ethylene in organic synthesis. Repetitive hydrovinylation of alkenes for highly enantioselective syntheses of pseudopterosins

Daniel J Mans  1 , G Adam Cox, T V RajanBabu
Affiliations

Ethylene in organic synthesis. Repetitive hydrovinylation of alkenes for highly enantioselective syntheses of pseudopterosins

Daniel J Mans et al. J Am Chem Soc. .

Abstract

In this report we highlight the significant potential of ethylene as a reagent for the introduction of a vinyl group with excellent stereoselectivity at three different stages in the synthesis of a broad class of natural products, best exemplified by syntheses of pseudopterosins. The late-stage applications of the asymmetric hydrovinylation reaction further illustrate the compatibility of the catalyst with complex functional groups. We also show that, depending on the choice of the catalyst, it is possible to either enhance or even completely reverse the inherent diastereoselectivity in the reactions of advanced chiral intermediates. This should enable the synthesis of diastereomeric analogs of several classes of medicinally relevant compounds that are not readily accessible by the existing methods, which depend on 'substrate control' for the installation of many of the chiral centers, especially in molecules of this class.

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Figures

Figure 1
Figure 1
Structures of Pseudopterosins and Related Compounds
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Stereoselective Synthesis of Pseudopterosin A-F Aglycone
Scheme 3
Scheme 3
Stereoselective Synthesis of Pseudopterosin G-J Aglycone via Installation of the C1 Side-chain Using Asymmetric Hydrovinylation
See this image and copyright information in PMC

References

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