Sulfinimines are important chiral auxiliaries for asymmetric synthesis of amines. Enantiopure sulfinimines can be prepared from the direct condensation of enantiopure sulfinamides with aldehydes or ketones. However, few sulfinamides are available in enantiomerically pure form. To make a wider range of sulfinamides, we examined hydrolase-catalyzed resolution of N-acylsulfinamides. Using a fast screening method, we identified several hydrolases that catalyzed the hydrolysis of N-chloroacetyl-p-toluenesulfinamide with high to moderate selectivity. Scale-up reaction identified proteinase from Bacillus subtilis var. biotecus A that reacted at the carbonyl position and showed high enantioselectivity (E > 150) favoring the (R)-N-chloroacetyl-p-toluenesulfinamide. This hydrolase provided a new route to enantiopure p-chlorobenzenesulfinamide, benzenesulfinamide, p-methoxybenzenesulfinamide and 2,4,6-trimethylbenzenesulfinamide that cannot be prepared from current methods. We also identified proteinase, bacterial, which hydrolyzed N-acylsulfinamide at the sulfinyl yielding p-toluenesulfinic acid. The reaction occurred with enantioselectivity (E' ∼ 75) and provided enantiopure (S)-N-chloroacetyl-p-toluenesulfinamide.* / *Please refer to dissertation for diagram.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.33803 |
| Date | January 2001 |
| Creators | Magloire, Vladimir P. |
| Contributors | Kazlauskas, Romas J. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Master of Science (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001873525, proquestno: MQ78920, Theses scanned by UMI/ProQuest. |
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