We report a highly cross- and atroposelective coupling between -(chloro)arylphosphine oxides and -(bromo)aryl ethers. This previously unknown asymmetric nickel-catalyzed reaction offers a direct route to highly enantioenriched axially chiral biaryl monophosphine oxides that are difficult to access by other means. These products can be readily reduced to generate chiral MOP-type ligands bearing complex skeletal backbones. The utility of these chiral ligands in asymmetric catalysis is also demonstrated.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11222061PMC
http://dx.doi.org/10.1021/jacs.4c04608DOI Listing

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We report a highly cross- and atroposelective coupling between -(chloro)arylphosphine oxides and -(bromo)aryl ethers. This previously unknown asymmetric nickel-catalyzed reaction offers a direct route to highly enantioenriched axially chiral biaryl monophosphine oxides that are difficult to access by other means. These products can be readily reduced to generate chiral MOP-type ligands bearing complex skeletal backbones.

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Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C-H functionalization of arylphosphine oxides. Involving C-H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework.

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MOP-phosphonites: a novel ligand class for asymmetric catalysis.

Dalton Trans

March 2012

School of Chemistry, Bedson Building, Newcastle University, Newcastle Upon Tyne, NE1 7RU, UK.

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[reaction: see text] Pd-catalyzed monophosphinylation of (R)-2-bromo-2'-iodo-1,1'-binaphthyl with Ph(2)P(O)H afforded (R)-2-bromo-2'-diphenylphosphinyl-1,1'-binaphthyl in good yield with excellent chemoselectivity and no observable racemization. Subsequent lithiation in the presence of excess thiosulfonate furnished an enantiomerically pure sulfenylation product, which was reduced to afford a chiral S-MOP ligand.

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