Diastereoselective Synthesis of (+/-)-1,2-Diphenyl-1,2-propanediol. A Discovery-Based Grignard Reaction Suitable for a Large Organic Lab Course
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James A. Ciaccio [1] ; Roxana P. Bravo [1] ; Antoinette L. Drahus [1] ; John B. Biggins [1] ; Rosalyn V. Concepcion [1] ; David Cabrera [1]
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[1] Fordam University, United States
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- Localización: Journal of chemical education, ISSN 0021-9584, Vol. 78, Nº 4, 2001, pág. 531
- Idioma: inglés
- Texto completo no disponible (Saber más ...)
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Resumen
We have developed an undergraduate organic laboratory experiment that probes the diastereoselectivity of the reaction between a Grignard reagent and a common, inexpensive α-chiral ketone. Students isolate a single diastereomer of (+/-)-1,2-diphenyl-1,2-propanediol by treatment of (+/-)-benzoin with MeMgI. Since the mp ranges of the two possible diol diastereomers differ by 10 °C, the reaction's diastereoselectivity can be established by mp determination alone, and it can be rationalized by the preferential addition of MeMgI to the least sterically hindered face of the carbonyl group in a rigid, five-membered cyclic intermediate (the "Cram chelate model"). This experiment is an interesting alternative to traditional Grignard experiments, is operationally straightforward and easily performed in large lab courses, and introduces students to π-facial discrimination by having them establish the stereochemical course of kinetically controlled nucleophilic addition to a carbonyl.
