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Modular Design of Chiral Conjugate-Base-Stabilized Carboxylic Acids: Catalytic Enantioselective [4 + 2] Cycloadditions of Acetals

https://doi.org/10.1021/jacs.0c07212

Zhu, Zhengbo; Odagi, Minami; Supantanapong, Nantamon; Xu, Weici; Saame, Jaan; Kirm, Helmi-Ulrika; Abboud, Khalil A.; Leito, Ivo; Seidel, Daniel (September 2020, Journal of the American Chemical Society)
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Highly Acidic Conjugate‐Base‐Stabilized Carboxylic Acids Catalyze Enantioselective oxa‐Pictet–Spengler Reactions with Ketals

https://doi.org/10.1002/ange.201912677

Zhu, Zhengbo; Odagi, Minami; Zhao, Chenfei; Abboud, Khalil A.; Kirm, Helmi Ulrika; Saame, Jaan; Lõkov, Märt; Leito, Ivo; Seidel, Daniel (December 2019, Angewandte Chemie)

Abstract Acyclic ketone‐derived oxocarbenium ions are involved as intermediates in numerous reactions that provide valuable products, however, they have thus far eluded efforts aimed at asymmetric catalysis. We report that a readily accessible chiral carboxylic acid catalyst exerts control over asymmetric cyclizations of acyclic ketone‐derived trisubstituted oxocarbenium ions, thereby providing access to highly enantioenriched dihydropyran products containing a tetrasubstituted stereogenic center. The high acidity of the carboxylic acid catalyst, which exceeds that of the well‐known chiral phosphoric acid catalyst TRIP, is largely derived from stabilization of the carboxylate conjugate base through intramolecular anion‐binding to a thiourea site.
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Highly Acidic Conjugate‐Base‐Stabilized Carboxylic Acids Catalyze Enantioselective oxa‐Pictet–Spengler Reactions with Ketals

https://doi.org/10.1002/anie.201912677

Zhu, Zhengbo; Odagi, Minami; Zhao, Chenfei; Abboud, Khalil A.; Kirm, Helmi Ulrika; Saame, Jaan; Lõkov, Märt; Leito, Ivo; Seidel, Daniel (December 2019, Angewandte Chemie International Edition)

Abstract Acyclic ketone‐derived oxocarbenium ions are involved as intermediates in numerous reactions that provide valuable products, however, they have thus far eluded efforts aimed at asymmetric catalysis. We report that a readily accessible chiral carboxylic acid catalyst exerts control over asymmetric cyclizations of acyclic ketone‐derived trisubstituted oxocarbenium ions, thereby providing access to highly enantioenriched dihydropyran products containing a tetrasubstituted stereogenic center. The high acidity of the carboxylic acid catalyst, which exceeds that of the well‐known chiral phosphoric acid catalyst TRIP, is largely derived from stabilization of the carboxylate conjugate base through intramolecular anion‐binding to a thiourea site.
more » « less

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