Application of Proline-Derived (Thio)squaramide Organocatalysts in Asymmetric Diels–Alder and Conjugate Addition Reactions

Gyula Dargó; Sándor Nagy; Dávid Kis; Péter Bagi; Béla Mátravölgyi; Blanka Tóth; Péter Huszthy; László Drahos; József Kupai

doi:10.1055/s-0040-1719886

Synthesis, Inhaltsverzeichnis

Synthesis 2022; 54(17): 3823-3830
DOI: 10.1055/s-0040-1719886

special topic

Special Issue in memory of Prof. Ferenc Fülöp

Application of Proline-Derived (Thio)squaramide Organocatalysts in Asymmetric Diels–Alder and Conjugate Addition Reactions

Gyula Dargó

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Sándor Nagy

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Dávid Kis

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Péter Bagi

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Béla Mátravölgyi

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Blanka Tóth

^bDepartment of Inorganic & Analytical Chemistry, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

Péter Huszthy

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

,

László Drahos

^cMS Proteomics Research Group, Research Centre for Natural Sciences, Magyar Tudósok körútja 2, 1117 Budapest, Hungary

,

József Kupai ∗

^aDepartment of Organic Chemistry & Technology, Budapest University of Technology & Economics, Szent Gellért tér 4, 1111 Budapest, Hungary

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Abstract

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Dedicated to the memory of Prof. Ferenc Fülöp

Abstract

The synthesis of chiral proline-derived squaramide and thiosquaramide organocatalysts, which are capable of the dual activation in asymmetric reactions is reported. The (thio)squaramide moiety can form hydrogen bonds to activate the substrates and to stereocontrol the reaction, while the pyrrolidine unit can form enamines to activate carbonyl compounds via aminocatalysis. Comparing the performance of thiosquaramide to squaramide, the Diels–Alder reaction of (anthracen-9-yl)acetaldehyde and trans-β-nitrostyrene was examined, which has been investigated in the literature using quantum chemical calculations. Both squaramide and thiosquaramide gave excellent yields (up to 99%) and enantiomeric excess values (up to 98%). Moreover, their catalytic performance was compared in conjugate addition of lawsone to β,γ-unsaturated α-keto ester.

Key words

asymmetric organocatalysis - aminocatalysis - proline - thiosquaramide - Diels–Alder reaction - conjugate addition

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Referenzen

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