EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK.
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR, 97331, USA.
Angew Chem Int Ed Engl. 2018 Mar 12;57(12):3200-3206. doi: 10.1002/anie.201712456. Epub 2018 Feb 19.
A combination of experimental and computational studies have identified a C=O⋅⋅⋅isothiouronium interaction as key to efficient enantiodiscrimination in the kinetic resolution of tertiary heterocyclic alcohols bearing up to three potential recognition motifs at the stereogenic tertiary carbinol center. This discrimination was exploited in the isothiourea-catalyzed acylative kinetic resolution of tertiary heterocyclic alcohols (38 examples, s factors up to >200). The reaction proceeds at low catalyst loadings (generally 1 mol %) with either isobutyric or acetic anhydride as the acylating agent under mild conditions.
实验和计算研究的结合确定了 C=O⋅⋅⋅异硫脲相互作用是在动力学拆分中有效对映体识别的关键，这些动力学拆分涉及到带有三个潜在识别基序的立体手性三级碳中心的三级杂环醇。这种识别在异硫脲催化的酰基化动力学拆分中得到了利用，涉及到三级杂环醇（38 个实例，s 因子高达>200）。该反应在低催化剂负载（通常为 1 mol%）下进行，使用异丁酸或乙酸酐作为酰化剂，在温和条件下进行。
