Asymmetric Conjugate Addition of α,α-Disubstituted Aldehydes to Nitroalkenes Organocatalyzed by Chiral Monosalicylamides from trans-Cyclohexane-1,2-Diamines

José R Martínez-Guillén; Jesús Flores-Ferrándiz; Cecilia Gómez; Enrique Gómez-Bengoa; Rafael Chinchilla

doi:10.3390/molecules23010141

Asymmetric Conjugate Addition of α,α-Disubstituted Aldehydes to Nitroalkenes Organocatalyzed by Chiral Monosalicylamides from trans-Cyclohexane-1,2-Diamines

Molecules. 2018 Jan 11;23(1):141. doi: 10.3390/molecules23010141.

Authors

José R Martínez-Guillén¹, Jesús Flores-Ferrándiz², Cecilia Gómez³, Enrique Gómez-Bengoa⁴, Rafael Chinchilla⁵

Affiliations

¹ Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain. jramonimg@gmail.com.
² Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain. jfloresf@gmail.com.
³ Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain. cgomez@ua.es.
⁴ Department of Organic Chemistry I, University of the Basque Country, P.O. Box 1072, 20080 San Sebastíán, Spain. enrique.gomez@ehu.es.
⁵ Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain. chinchilla@ua.es.

Abstract

Primary amine-salicylamides derived from chiral trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to arylated and heteroarylated nitroalkenes. The reaction is performed in the presence of 4-dimethylaminopyridine as an additive in dichloromethane as a solvent at room temperature. The corresponding enantioenriched γ-nitroaldehydes are obtained with enantioselectivities up to 95%. Theoretical calculations are used to justify the reasons of the stereoinduction.

Keywords: Michael addition; asymmetric synthesis; nitroalkenes; organocatalysis.

MeSH terms

Aldehydes / chemistry*
Alkenes / chemistry*
Catalysis
Chemistry Techniques, Synthetic
Cyclohexanes / chemistry*
Cyclohexylamines / chemistry*
Diamines / chemistry*
Models, Chemical
Molecular Structure
Nitro Compounds / metabolism*
Stereoisomerism

Substances

Aldehydes
Alkenes
Cyclohexanes
Cyclohexylamines
Diamines
Nitro Compounds
Cyclohexane
1,2-cyclohexanediamine