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Chan YC, Sak MH, Frank SA, et al. Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes. Angew Chem Int Ed Engl. 2021;60(46):24573-24581doi: 10.1002/anie.202109694.
Chan, Y. C., Sak, M. H., Frank, S. A., & Miller, S. J. (2021). Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes. Angewandte Chemie (International ed. in English), 60(46), 24573-24581. https://doi.org/10.1002/anie.202109694
Chan, Yuk-Cheung, et al. "Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes." Angewandte Chemie (International ed. in English) vol. 60,46 (2021): 24573-24581. doi: https://doi.org/10.1002/anie.202109694
Chan YC, Sak MH, Frank SA, Miller SJ. Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes. Angew Chem Int Ed Engl. 2021 Nov 08;60(46):24573-24581. doi: 10.1002/anie.202109694. Epub 2021 Oct 07. PMID: 34487418; PMCID: PMC8556314.
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Angew Chem Int Ed Engl. 2021 Nov 08;60(46):24573-24581. doi: 10.1002/anie.202109694. Epub 2021 Oct 07.

Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes.

Angewandte Chemie (International ed. in English)

Yuk-Cheung Chan, Marcus H Sak, Scott A Frank, Scott J Miller

Affiliations

  1. Department of Chemistry, Yale University, New Haven, CT, 06520, USA.
  2. Synthetic Molecule Design and Development, Eli Lilly and Company, Indianapolis, IN, 46285, USA.

PMID: 34487418 PMCID: PMC8556314 DOI: 10.1002/anie.202109694

Abstract

Herein we report an organocatalytic enantioselective functionalization of heterocyclic carboxaldehydes via the Pictet-Spengler reaction. Through careful pairing of novel squaramide and Brønsted acid catalysts, our method tolerates a breadth of heterocycles, enabling preparation of a series of heterocycle conjugated β-(tetrahydro)carbolines in good yield and enantioselectivity. Careful selection of carboxylic acid co-catalyst is essential for toleration of a variety of regioisomeric heterocycles. Utility is demonstrated via the three-step stereoselective preparation of pyridine-containing analogues of potent selective estrogen receptor downregulator and U.S. FDA approved drug Tadalafil.

© 2021 Wiley-VCH GmbH.

Keywords: Pictet-Spengler; cooperative catalysis; heterocycles; hydrogen bond donors; peptides

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