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Resolution of aryl-H-phosphinates applied in the synthesis of P-stereogenic compounds including a Brønsted acid NMR solvating agent
A library of racemic H-phosphinates incorporating a variety of alkoxy groups or substituted aryl groups was prepared. Starting with resolving agent screening, an efficient enantioseparation method was developed and optimized using (R,R)-(1-naphthyl)-spiro-TADDOL as the resolving agent. This method g...
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Published in: | Organic chemistry frontiers an international journal of organic chemistry 2022-05, Vol.9 (10), p.2797-2807 |
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Main Authors: | , , , , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that cite this one |
Online Access: | Get full text |
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Summary: | A library of racemic H-phosphinates incorporating a variety of alkoxy groups or substituted aryl groups was prepared. Starting with resolving agent screening, an efficient enantioseparation method was developed and optimized using (R,R)-(1-naphthyl)-spiro-TADDOL as the resolving agent. This method gave 12 out of 16 H-phosphinates with an ee of above 91%, and 9 of these derivatives were practically enantiopure (ee > 98%). Moreover, this resolution could be used on a gram-scale. The structures of the diastereomeric intermediates and the secondary interactions between them were investigated by single-crystal XRD, and the most important factors of enantiomeric recognition were established. (R)-1-Adamantyl phenyl-H-phosphinate was stereospecifically transformed into a few secondary and tertiary phosphine oxides. Moreover, two P-stereogenic Brønsted acids were prepared, and their applicability as chiral NMR solvating agents was assessed. |
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ISSN: | 2052-4110 2052-4110 |
DOI: | 10.1039/d2qo00241h |