Kinetic Resolution of Amines: A Highly Enantioselective and Chemoselective Acetylating Agent with a Unique Solvent-Induced Reversal of Stereoselectivity†
Stellios Arseniyadis Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
Search for more papers by this authorAlain Valleix
CEA Saclay, Service des molecules marquées 91191 Gif sur Yvette, France
Search for more papers by this authorAlain Wagner Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
Search for more papers by this authorCharles Mioskowski Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
CEA Saclay, Service des molecules marquées 91191 Gif sur Yvette, France
Search for more papers by this authorStellios Arseniyadis Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
Search for more papers by this authorAlain Valleix
CEA Saclay, Service des molecules marquées 91191 Gif sur Yvette, France
Search for more papers by this authorAlain Wagner Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
Search for more papers by this authorCharles Mioskowski Dr.
Laboratoire de Synthèse Bioorganique, UMR 7514 du CNRS, Faculté de Pharmacie, 74 route du Rhin, 67400 Illkirch, France, Fax: (+33) 3-9024-4306
CEA Saclay, Service des molecules marquées 91191 Gif sur Yvette, France
Search for more papers by this authorWe thank Rhodia for financial support to S.A., as well as Dr. A. De Cian and Dr. N. Gruber for their helpful collaborations in the collection of the X-ray crystallographic data.
Graphical Abstract
Solvents lend a hand: Changing the polarity of the reaction solvent from 1,3-dimethyltetrahydropyrimidin-2-one (DMPU) to toluene reverses the stereoselectivity observed in the acetylation of amines with (1S,2S)-1 (see scheme). Optimizing the reaction conditions led to an unprecedented 90 % ee (S) in DMPU at −20 °C with a 33 % conversion.
Supporting Information
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