Cleavage of P=O in the Presence of P-N: Aminophosphine Oxide Reduction with In Situ Boronation of the PIII Product

Files in This Item:
File Description SizeFormat 
KennyetalCEJ_V7.pdf206.94 kBAdobe PDFDownload
Title: Cleavage of P=O in the Presence of P-N: Aminophosphine Oxide Reduction with In Situ Boronation of the PIII Product
Authors: Kenny, Niall P.
Rajendran, Kamalraj V.
Jennings, Elizabeth V.
Gilheany, Declan G.
Permanent link:
Date: 11-Oct-2013
Abstract: In contrast to tertiary phosphine oxides, the deoxygenation of aminophosphine oxides is effectively impossible due to the need to break the immensely strong and inert PO bond in the presence of a relatively weak and more reactive PN bond. This long-standing problem in organophosphorus synthesis is solved by use of oxalyl chloride, which chemoselectively cleaves the PO bond forming a chlorophosphonium salt, leaving the PN bond(s) intact. Subsequent reduction of the chlorophosphonium salt with sodium borohydride forms the PIII aminophosphine borane adduct. This simple one-pot procedure was applied with good yields for a wide range of PN-containing phosphoryl compounds. The borane product can be easily deprotected to produce the free PIII aminophosphine. Along with no observed PN bond cleavage, the use of sodium borohydride also permits the presence of ester functional groups in the substrate. The availability of this methodology opens up previously unavailable synthetic options in organophosphorus chemistry, two of which are exemplified.
Type of material: Journal Article
Publisher: Wiley-VCH
Copyright (published version): 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Keywords: Aminophosphine oxideChemoselectivityIn situ protectionMain group elementsReduction
DOI: 10.1002/chem.201302907
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

Show full item record

Citations 20

Last Week
Last month
checked on Sep 17, 2018

Page view(s) 50

checked on May 25, 2018

Download(s) 20

checked on May 25, 2018

Google ScholarTM



This item is available under the Attribution-NonCommercial-NoDerivs 3.0 Ireland. No item may be reproduced for commercial purposes. For other possible restrictions on use please refer to the publisher's URL where this is made available, or to notes contained in the item itself. Other terms may apply.