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. 2006 Feb 15;128(6):1840-6.
doi: 10.1021/ja055994d.

Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis

Timothy W Funk  1 , Jacob M Berlin, Robert H Grubbs
Affiliations

Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis

Timothy W Funk et al. J Am Chem Soc. .

Abstract

The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) are reported. These catalysts retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings (catalysts 3-5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium iodide to catalysts 2a-4a (to form 2b-4b in situ) caused a dramatic increase in enantioselectivity for many substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition of NaI, could be used in loadings of < or =1 mol %. Mechanistic explanations for the large sodium iodide effect as well as possible mechanistic pathways leading to the observed products are discussed.

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Figures

Figure 1
Figure 1
Solvent Effect on Enantioselectivity of ARCM.
Figure 2
Figure 2
Temperature Effect on Enantioselectivity of ARCM.
Figure 3
Figure 3
Ethylenolysis of 12.
Figure 4
Figure 4
Suggested Alkylidene Position in trans-Binding Transition State.
Scheme 1
Scheme 1
Synthesis of Chiral Ruthenium Olefin Metathesis Catalysts.
Scheme 2
Scheme 2
Proposed Pathways Leading to the Desired Product.
Chart 1
Chart 1
Ruthenium Olefin Metathesis Catalysts.
See this image and copyright information in PMC

References

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