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Robinson ERT, Walden DM, Fallan C, et al. Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles. Chem Sci. 2016;7(12):6919-6927doi: 10.1039/c6sc00940a.
Robinson, E. R. T., Walden, D. M., Fallan, C., Greenhalgh, M. D., Cheong, P. H., & Smith, A. D. (2016). Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles. Chemical science, 7(12), 6919-6927. https://doi.org/10.1039/c6sc00940a
Robinson, Emily R T, et al. "Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles." Chemical science vol. 7,12 (2016): 6919-6927. doi: https://doi.org/10.1039/c6sc00940a
Robinson ERT, Walden DM, Fallan C, Greenhalgh MD, Cheong PH, Smith AD. Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles. Chem Sci. 2016 Dec 01;7(12):6919-6927. doi: 10.1039/c6sc00940a. Epub 2016 Jul 04. PMID: 28567263; PMCID: PMC5450589.
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Chem Sci. 2016 Dec 01;7(12):6919-6927. doi: 10.1039/c6sc00940a. Epub 2016 Jul 04.

Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles.

Chemical science

Emily R T Robinson, Daniel M Walden, Charlene Fallan, Mark D Greenhalgh, Paul Ha-Yeon Cheong, Andrew D Smith

Affiliations

  1. EaStCHEM , School of Chemistry , University of St Andrews , North Haugh , St Andrews KY16 9ST , UK . Email: [email protected].
  2. Department of Chemistry , Oregon State University , 135 Gilbert Hall , Corvallis , OR 97331 , USA . Email: [email protected].

PMID: 28567263 PMCID: PMC5450589 DOI: 10.1039/c6sc00940a

Abstract

Isothiourea-catalyzed annulations between 2-acyl benzazoles and α,β-unsaturated acyl ammonium intermediates are selectively tuned to form either lactam or lactone heterocycles in good yields (up to 95%) and high ee (up to 99%) using benzothiazole or benzoxazole derivatives, respectively. Computation gives insight into the significant role of two 1,5-S···O interactions in controlling the structural preorganization and chemoselectivity observed within the lactam synthesis with benzothiazoles as nucleophiles. When using benzazoles the absence of a second stabilizing non-bonding 1,5-S···O interaction leads to a dominant C-H···O interaction in determining structural preorganization and lactone formation.

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