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Identification of a key intermediate in the asymmetric Appel process: one pot stereoselective synthesis of P-stereogenic phosphines and phosphine boranes from racemic phosphine oxides
Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin, Dublin 4, Ireland
E-mail: declan.gilheany@ucd.ie
; Fax: +353-1-7162127
; Tel: +353-1-7162308
Chem. Commun., 2012,48, 10040-10042
DOI:
10.1039/C2CC34136K
Received
08 Jun 2012,
Accepted
15 Aug 2012
First published online
16 Aug 2012
Sequential treatment of racemic phosphine oxides with oxalyl chloride and chiral non-racemic alcohol generates the same ratios of diastereomeric alkoxyphosphonium salts obtained in the corresponding asymmetric Appel process, strongly implicating the intermediate chlorophosphonium salt in the stereoselecting step. Subsequent reduction allows a novel synthesis of enantioenriched P-stereogenic phosphines–phosphine boranes.
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