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://dx.doi.org/10.1021/jacs.4c04608 | DOI Listing |
J Am Chem Soc
July 2024
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.
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.
View Article and Find Full Text PDFOrg Lett
October 2017
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China.
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.
View Article and Find Full Text PDFDalton Trans
March 2012
School of Chemistry, Bedson Building, Newcastle University, Newcastle Upon Tyne, NE1 7RU, UK.
Chiral phosphonite ligands (S,R(b))-5a, (S,S(b))-5b, (R,R(b))-6a and (R,S(b))-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η(3)-C(4)H(7))Cl](2) affords η(3)-methallylpalladium chloride complexes 7a/b and 8a/b which have been isolated and structurally characterised. Solid-state and solution studies indicate subtle differences in their coordination behaviour, which ultimately affects their efficacy in the asymmetric hydrosilylation of styrene.
View Article and Find Full Text PDFJ Org Chem
August 2006
School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, 800 Dongchuan Road, Shanghai 200240, China.
A series of 2-dialkylphosphino-2'-alkoxy-1,1'-binaphthyl ligands (6a-c and 8a-c) have been prepared conveniently by a lithium-initiated ring-opening reaction of dinaphthofuran, followed by selective phosphorylation. These compounds displayed a remarkable air and moisture stability, both in solid form and in solution. Application of these phosphine ligands in palladium-catalyzed C-N bond forming reactions revealed the crucial roles of the steric bulk of the substituents on the phosphorus atom governing the catalytic activity.
View Article and Find Full Text PDFJ Org Chem
October 2005
Faculty of Engineering, Niigata University, Ikarashi, Japan.
[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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