Organophosphorus‐Catalysed Staudinger Reduction

Abstract

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A high‐efficient method for the amidation of carboxylic acids promoted by triphenylphosphine oxide and oxalyl chloride

“…Such in situ reduction of phosphorus oxides has been exployed in several catalytic reaction, as the pioneer work of catalytic Wittig reaction by O'Brien and co‐workers, and van Delft et al. developed the first catalytic Appel and Staudinger reaction. This technique is effective, but its operating cost is high because of the harsh reagents and conditions required to regenerate phosphines and the complexity of the reaction system.…”

“…To overcome these drawbacks, Mecinovi′c [21] reported an organocatalytic amide bond formation reaction mediated by Ph 3 P/CCl 4 ; in this reaction, TPPO is reduced into Ph 3 P in situ (Scheme 2). Such in situ reduction of phosphorus oxides has been exployed in several catalytic reaction, as the pioneer work of catalytic Wittig reaction by O'Brien and coworkers [22][23][24][25] , and van Delft et al developed the first catalytic Appel and Staudinger reaction [26,27] . This technique is effective, but its operating cost is high because of the harsh reagents and conditions required to regenerate phosphines and the complexity of the reaction system.…”

Catalytic Wittig and aza-Wittig reactions

“…The initial research in this area was performed by Floris L. van Delft and co-workers who reported the synthesis of 61 and its use in catalytic Staudinger reactions for the reduction of azides 62 to amines 63 (Scheme 17) [34]. Subsequently they extended such reactions to include aza-Wittig reactions using diphenylsilane as the reducing reagent [35].…”

Recyclable Polymer-Supported Terpyridine–Palladium Complex for the Tandem Aminocarbonylation of Aryl Iodides to Primary Amides in Water Using NaN3 as Ammonia Equivalent

“…Transformation of A to B takes place via ligand exchange followed by reductive elimination, which produces complex C. The reaction of C with CO gas afforded terpy-Pd 0 (CO) and the azidocarbonylation product (ArCON 3 ), which is used in the catalytic Staudinger reaction shown in cycle 2 of Scheme 3 [29]. Thus, the oxidative addition of ArCON 3 to terpy-Pd 0 (CO) yields the palladacycle D followed by the reductive elimination of D to form E, which is transformed to the primary amide in water under CO gas.…”