1. Improved Synthetic Route to Heteroleptic Alkylphosphine Oxides
- Author
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Daniel T. Seidenkranz, Alexander J. Kendall, and David R. Tyler
- Subjects
chemistry.chemical_classification ,Phosphinite ,010405 organic chemistry ,ved/biology ,Organic Chemistry ,ved/biology.organism_classification_rank.species ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Deprotonation ,Nucleophile ,chemistry ,Amide ,Organic chemistry ,SN2 reaction ,Physical and Theoretical Chemistry ,Alkyl ,Phosphine ,Conjugate acid - Abstract
A new method for the synthesis of heteroleptic alkylphosphine oxides (R2R1P═O, where R ≠ R1) from secondary phosphine oxides (or SPOs, R2HP═O) is presented. These reactions were fast at room temperature, sterically selective, high yielding, and >95% pure after an aqueous wash. Deprotonation of an SPO generates a phosphinite anion ([R2P–O]−) that was found to be highly selective for nucleophilic P–C bond formation (as opposed to O–C bond formation) with alkyl halides. Surprisingly, most strong organometallic bases failed to deprotonate SPOs to their respective phosphinite anions (pKas for most SPOs are
- Published
- 2017