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Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes.
J Org Chem. 2015 Jun 05; 80(11):5588-99.JO

Abstract

Homochiral methyl 4-aminopyrrolidine-2-carboxylates are readily obtained by means of asymmetric (3 + 2) cycloadditions between azomethine ylides and nitroalkenes, followed by catalytic hydrogenation of the intermediate 4-nitro cycloadducts. These 4-aminopyrrolidine-2-carboxylate esters belong to the L-series of natural amino acids and catalyze asymmetric Michael additions of ketones to nitroalkenes. However, the enantioselectivity observed with these novel unnatural organocatalysts is opposite to that obtained with L-proline. Since both 4-nitro and 4-amino L-proline esters are efficient organocatalysts of aldol reactions, these results permit to modulate asymmetric quimioselective aldol and conjugate addition reactions.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Ruiz-Olalla A
†Departamento de Química Orgánica I/Kimika Organiko I Saila, Universidad del País Vasco/Euskal Herriko Unibertsitatea, and Centro de Innovación en Química Avanzada (ORFEO-CINQA), P° Manuel Lardizabal 3, 20018 San Sebastián/Donostia, Gipuzkoa, Spain.
Retamosa Mde G
†Departamento de Química Orgánica I/Kimika Organiko I Saila, Universidad del País Vasco/Euskal Herriko Unibertsitatea, and Centro de Innovación en Química Avanzada (ORFEO-CINQA), P° Manuel Lardizabal 3, 20018 San Sebastián/Donostia, Gipuzkoa, Spain. ‡Donostia International Physics Center (DIPC), P° Manuel Lardizabal 4, 20018 San Sebastián/Donostia, Gipuzkoa, Spain.
Cossío FP
†Departamento de Química Orgánica I/Kimika Organiko I Saila, Universidad del País Vasco/Euskal Herriko Unibertsitatea, and Centro de Innovación en Química Avanzada (ORFEO-CINQA), P° Manuel Lardizabal 3, 20018 San Sebastián/Donostia, Gipuzkoa, Spain. ‡Donostia International Physics Center (DIPC), P° Manuel Lardizabal 4, 20018 San Sebastián/Donostia, Gipuzkoa, Spain.

MeSH

AlkenesCatalysisCycloaddition ReactionEstersKetonesMolecular StructureNitro CompoundsProlineStereoisomerism

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

25974363

Citation

Ruiz-Olalla, Andrea, et al. "Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes." The Journal of Organic Chemistry, vol. 80, no. 11, 2015, pp. 5588-99.
Ruiz-Olalla A, Retamosa Mde G, Cossío FP. Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes. J Org Chem. 2015;80(11):5588-99.
Ruiz-Olalla, A., Retamosa, M. d. e. . G., & Cossío, F. P. (2015). Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes. The Journal of Organic Chemistry, 80(11), 5588-99. https://doi.org/10.1021/acs.joc.5b00495
Ruiz-Olalla A, Retamosa Mde G, Cossío FP. Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes. J Org Chem. 2015 Jun 5;80(11):5588-99. PubMed PMID: 25974363.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes. AU - Ruiz-Olalla,Andrea, AU - Retamosa,María de Gracia, AU - Cossío,Fernando P, Y1 - 2015/05/27/ PY - 2015/5/15/entrez PY - 2015/5/15/pubmed PY - 2016/3/2/medline SP - 5588 EP - 99 JF - The Journal of organic chemistry JO - J Org Chem VL - 80 IS - 11 N2 - Homochiral methyl 4-aminopyrrolidine-2-carboxylates are readily obtained by means of asymmetric (3 + 2) cycloadditions between azomethine ylides and nitroalkenes, followed by catalytic hydrogenation of the intermediate 4-nitro cycloadducts. These 4-aminopyrrolidine-2-carboxylate esters belong to the L-series of natural amino acids and catalyze asymmetric Michael additions of ketones to nitroalkenes. However, the enantioselectivity observed with these novel unnatural organocatalysts is opposite to that obtained with L-proline. Since both 4-nitro and 4-amino L-proline esters are efficient organocatalysts of aldol reactions, these results permit to modulate asymmetric quimioselective aldol and conjugate addition reactions. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/25974363/Densely_Substituted_L_Proline_Esters_as_Catalysts_for_Asymmetric_Michael_Additions_of_Ketones_to_Nitroalkenes_ DB - PRIME DP - Unbound Medicine ER -