Isothiourea‐Catalyzed Acylative Kinetic Resolution of Tertiary α‐Hydroxy Esters

Abstract: A highly enantioselective isothiourea‐catalyzed acylative kinetic resolution (KR) of acyclic tertiary alcohols has been developed. Selectivity factors of up to 200 were achieved for the KR of tertiary alcohols bearing an adjacent ester substituent, with both reaction conversion and enantioselectivity found to be sensitive to the steric and electronic environment at the stereogenic tertiary carbinol centre. For more sterically congested alcohols, the use of a recently‐developed isoselenourea catalyst was optimal, with equivalent enantioselectivity but higher conversion achieved in comparison to the isothiourea HyperBTM. Diastereomeric acylation transition state models are proposed to rationalize the origins of enantiodiscrimination in this process. This KR procedure was also translated to a continuous‐flow process using a polymer‐supported variant of the catalyst.

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch

References and Relationships

• Bibliographic citation: Isothiourea‐Catalyzed Acylative Kinetic Resolution of Tertiary α‐Hydroxy Esters ; volume:59 ; number:38 ; year:2020 ; pages:16572-16578 ; extent:7 ; Angewandte Chemie / International edition. International edition ; 59, Heft 38 (2020), 16572-16578 (gesamt 7)

Contributors, Places and Time

• Creator: Qu, Shen ; Smith, Samuel M. ; Laina‐Martín, Víctor ; Neyyappadath, Rifahath M. ; Greenhalgh, Mark ; Smith, Andrew D.

Further information

• DOI: 10.1002/anie.202004354
• URN: urn:nbn:de:101:1-2022061212591642870903
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 15.08.2025, 7:26 AM CEST