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Synthesis 2015; 47(14): 2063-2072
DOI: 10.1055/s-0034-1380203
DOI: 10.1055/s-0034-1380203
paper
Highly Enantioselective Michael Addition of Nitroalkanes to Enones and Its Application in Syntheses of (R)-Baclofen and (R)-Phenibut
Further Information
Publication History
Received: 23 January 2015
Accepted after revision: 22 March 2015
Publication Date:
19 May 2015 (online)
Abstract
A highly enantioselective Michael addition of nitroalkanes to α,β-unsaturated ketones was developed. In the presence of a chiral primary amine–thiourea catalyst based on dehydroabietic amine, γ-nitro ketones were obtained with excellent enantioselectivities (up to 99% ee) and in up to 96% yield. This protocol was successfully applied in asymmetric syntheses of (R)-baclofen and (R)-phenibut with high yields and excellent enantioselectivities.
Key words
chiral primary amine–thiourea - dehydroabietic amine - enantioselective Michael addition - nitroalkanes - α,β-unsaturated ketonesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380203.
- Supporting Information
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References and Notes
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For selected examples, see:
For selected reviews, see:
For examples of organocatalytic enantioselective Michael additions of nitroalkanes to chalcones, see:
For examples of the organocatalytic enantioselective Michael additions of nitroalkanes to cyclic enones, see:
For examples of the organocatalytic enantioselective Michael additions of nitroalkanes to alkyl cinnamyl ketones, see:
For application of chiral primary amine–thiourea compounds based on dehydroabietic amine, see:
For applications of cyclohexanediamine-derived chiral tertiary amine–thiourea compounds based on dehydroabietic amine, see:
For applications of cinchona alkaloid-derived chiral tertiary amine–thiourea compounds based on dehydroabietic amine, see:
For selected examples of analogous Michael reactions of enones and C-nucleophiles, e.g. malonates, catalyzed by the same type of catalyst based on primary amine–thiourea compounds derived from cyclohexane-1,2-diamine, see:
For selected examples of the synthesis of compound 4aa through the organocatalyzed Michael addition of acetone to p-chloronitrostyrene with high yield and excellent enantioselectivities, see:
For the comparative pharmacological activities of the two enantiomers of baclofen, see:
For the comparative pharmacological activities of the two enantiomers of phenibut, see:
For selected examples of asymmetric syntheses of (R)-baclofen and (R)-phenibut using chiral organocatalysts, see:
For selected examples of asymmetric syntheses of (R)-baclofen and (R)-phenibut using chiral organometallic catalysts, see: