New enantiopure binaphthyl-cinchona thiosquaramides: synthesis and application for enantioselective organocatalysis

This work presents the first successful applications of cinchona-thiosquaramides in asymmetric reactions. Binaphthyl-cinchona squaramides and thiosquaramides were synthesised, and then used as organocatalysts to promote the catalytic enantioselective Michael addition reaction of pentane-2,4-dione to...

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Published in:New journal of chemistry 2019, Vol.43 (15), p.5948-5959
Main Authors: Nagy, Sándor, Dargó, Gyula, Kisszékelyi, Péter, Fehér, Zsuzsanna, Simon, András, Barabás, Júlia, Höltzl, Tibor, Mátravölgyi, Béla, Kárpáti, Levente, Drahos, László, Huszthy, Péter, Kupai, József
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Subjects:
Adducts
Catalysis
Catalysts
Chemical synthesis
Conjugates
Enantiomers
Michael reaction
NMR
Nuclear magnetic resonance
Organic chemistry
Quantum chemistry
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creator Nagy, Sándor
Dargó, Gyula
Kisszékelyi, Péter
Fehér, Zsuzsanna
Simon, András
Barabás, Júlia
Höltzl, Tibor
Mátravölgyi, Béla
Kárpáti, Levente
Drahos, László
Huszthy, Péter
Kupai, József
description This work presents the first successful applications of cinchona-thiosquaramides in asymmetric reactions. Binaphthyl-cinchona squaramides and thiosquaramides were synthesised, and then used as organocatalysts to promote the catalytic enantioselective Michael addition reaction of pentane-2,4-dione to trans -β-nitrostyrene with excellent yields (up to 99%) and enantioselectivities (up to 99% ee) at as low as 0.2 mol% catalyst loadings. Thiosquaramides gave higher enantioselectivities (up to 92% ee) in conjugate addition reaction of lawsone to β,γ-unsaturated α-keto ester than its oxo analogue, with high yields (up to 100%). Also, only thiosquaramide could catalyse the aza-Diels–Alder addition reaction of 2-siloxydiene to benzylideneacetone. Furthermore, quantum chemical computations showed that the geometrical structure of binaphthyl-cinchona thiosquaramide is similar to that of squaramide.
doi_str_mv 10.1039/C8NJ06451B
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subjects Adducts
Catalysis
Catalysts
Chemical synthesis
Conjugates
Enantiomers
Michael reaction
NMR
Nuclear magnetic resonance
Organic chemistry
Quantum chemistry
title New enantiopure binaphthyl-cinchona thiosquaramides: synthesis and application for enantioselective organocatalysis
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