Synthesis of Adamantyl H‐Phosphinate Esters

Adamantyl H‐phosphinate esters have been described by Leclaire, Giordano, and coworkers as “universal precursors of P‐stereogenic compounds” after resolution by chiral HPLC, because these esters resist racemization during displacement with organometallics. In that work, the racemic esters were prepa...

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Bibliographic Details
Published in:European journal of organic chemistry 2022-01, Vol.2022 (1), p.n/a
Main Authors: Winters, Karen R., Ricke, Chloe, Montchamp, Jean‐Luc
Format: Article
Language:English
Subjects:
Adamantyl ester
Chlorides
Esterification
Esters
H-Phosphinate
High performance liquid chromatography
Organometallic compounds
Precursors
Racemization
Synthesis
Synthesis design
Synthetic methods
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Summary:Adamantyl H‐phosphinate esters have been described by Leclaire, Giordano, and coworkers as “universal precursors of P‐stereogenic compounds” after resolution by chiral HPLC, because these esters resist racemization during displacement with organometallics. In that work, the racemic esters were prepared from phosphorus trichloride or dichlorophosphines (RPCl2). We decided to investigate alternative methods for the preparation of these important precursors. Esterification methods included EDC, PivCl, and T3P. A protocol to avoid chromatographic purification was also developed and used for multigram‐scale synthesis. Finally, adamantyl hypophosphite 1‐AdOP(O)H2 was also prepared and used in the synthesis adamantyl H‐phosphinate esters, thereby providing an alternative to the esterification of H‐phosphinic acids, although 1‐AdOP(O)H2 was much less reactive than other hypophosphite esters. Herein described several methods for the preparation of 1‐adamantyl H‐phosphinate esters. Either H‐phosphinic acids are esterified with 1‐adamantanol, or adamantyl hypophosphite reacts through phosphorus‐carbon bond‐formation. Adamantyl esters are significantly less reactive than their primary or secondary alkyl counterparts.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202101130