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Synfacts 2017; 13(12): 1286
DOI: 10.1055/s-0036-1591675
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Iridium-Catalyzed C–H Amidation of Diaryl Phosphine Oxides

Contributor(s):
Mark Lautens
,
Andrew Whyte
Jang Y.-S. Dieckmann M. Cramer N. * École Polytechnique Fédérale de Lausanne, Switzerland
Cooperative Effects between Chiral Cpx–Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C–H Amidations of Phosphine Oxides.

Angew. Chem. Int. Ed. 2017;
56: 15088-15092
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Publication History

Publication Date:
17 November 2017 (online)

 
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Key words

iridium catalysis - phosphine oxides - desymmetrization - amidation

Significance

The synthesis of chiral phosphorus compounds is always of interest because they are crucial as ligands for asymmetric catalysis. Cramer and co-workers report the desymmetrization of diaryl phosphine oxides through iridium-catalyzed amidation. The reaction used a chiral iridium and chiral acid acting cooperatively, which was dem-onstrated through a match and mismatch effect.


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Comment

The reaction tolerates some variation of substitution on the aryl rings and works best with bulky alkyl substitution on the phosphorus. Other sulfonates could be incorporated. The reaction proceeds through a C–H activation catalyzed by the chiral acid bound iridium complex followed by aryl amidation by the sulfonyl azide.


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