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Synfacts 2014; 10(1): 0051
DOI: 10.1055/s-0033-1340449
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Nickel-Catalyzed Hydrocarbamoylation of Alkenes

Contributor(s):
Mark Lautens
,
Christine M. Le
Donets PA, Cramer N * École Polytechnique Fédérale de Lausanne, Switzerland
Diaminophosphine Oxide Ligand Enabled Asymmetric Nickel-Catalyzed Hydrocarbamoylations of Alkenes.

J. Am. Chem. Soc. 2013;
135: 11772-11775
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Further Information

Publication History

Publication Date:
13 December 2013 (online)

 
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Key words

hydrocarbamoylation - phosphine oxide ligands - bimetallic catalysis

Significance

Secondary phosphine oxides (SPO’s) have demonstrated to be versatile and robust pre-ligands in a variety of transition-metal-catalyzed transformations due to their stability to air and moisture (see Review below). The authors report the development of a heterobimetallic catalyst system consisting of aluminum and nickel scaffolded on a chiral SPO tether, which enables the enantio­selective intramolecular hydrocarbamoylation of alkenes. This method provides access to enantioenriched pyrrolidones.


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Review

N. V. Dubrovina, A. Börner Angew. Chem. Int. Ed. 2004, 43, 5883–5886.


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Comment

The reaction is believed to initiate via tautomerization of pentavalent phosphine oxide 2 to its trivalent phosphinous acid form, 2′, which can react with Me3Al and form complex A. Coordination to nickel(0) generates the active heterobimetallic catalyst B, which complexes to substrate 1a via the Lewis acidic aluminum center, activating the formyl group towards insertion. Following oxidative addition of nickel into the C–H bond, migratory insertion of the pendent olefin and reductive elimination regenerate the catalyst and furnish pyrrolidone 3a.


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