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DOI: 10.1055/s-0035-1560658
Diastereoselective Synthesis of Trisubstituted Cyclopropanes by Palladium-Catalyzed Intramolecular Allylic Alkylation of α-Aryl Esters
Publikationsverlauf
Received: 12. August 2015
Accepted after revision: 16. September 2015
Publikationsdatum:
29. September 2015 (online)
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Abstract
We have developed a novel method for synthesizing trisubstituted cyclopropane derivatives by a palladium-catalyzed intramolecular allylic alkylation of α-aryl esters. By using α-aryl α-(methoxycarbonyl) γ-vinyl γ-lactones as substrates, decarboxylative formation of π-allylpalladium(II) intermediates followed by an intramolecular allylic alkylation of the ester enolates proceeded in the presence of 5 mol% of a palladium catalyst, producing 1-aryl-1-(methoxycarbonyl)-2-vinylcyclopropanes in good to excellent yields and high diastereoselectivities. The relative configuration of the major isomer was determined by transforming the product into a known intermediate of milnacipran synthesis. When we extended our method to asymmetric catalysis, we obtained methyl (1S,2S)-1-phenyl-2-vinylcyclopropanecarboxylate in up to 55% ee by using (S)-[2′-(diphenylmethoxy)-1,1′-binaphthalen-2-yl](diphenyl)phosphine as a chiral monodentate phosphorus ligand.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560658.
- Supporting Information
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For reviews, see:
For α-amino ester derivatives as nucleophiles, see:
For ester enolate equivalents as nucleophiles, see:
For α-aryl esters as nucleophiles, see:
For transition-metal-catalyzed intramolecular allylic alkylations to synthesize trisubstituted cyclopropanes by using malonate derivatives as substrates, see:
See also:
For representative examples of the synthesis of milnacipran and related compounds, see:
For recent representative examples of syntheses of trisubstituted cyclopropane derivatives, see:
For reviews on stereoselective synthesis of cyclopropane derivatives, see: