Formation of aryl dialkylphosphinates from dialkylphosphinous chlorides and arylmagnesium bromides under oxidative conditions

Keglevich, György; Tamás, Annamária; Parlagh, Gyula; Tőke, Lásʐló

doi:10.1002/1098-1071(2001)12:1<38::aid-hc8>3.3.co;2-j

Cited by 3 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We believe that these species are phosphine oxides. The shift at 51.0 ppm is reminiscent of the reported shift for Pr i 2 PhP(O) at 51.4 ppm in CDCl 3 . GC-MS of the catalysis samples also shows a species with m / z 210.…”

mentioning

confidence: 53%

Insights into the Heck Reaction with PCP Pincer Palladium(II) Complexes

2004

View full text Add to dashboard Cite

[reaction: see text] The Heck reaction of phenyl halides with styrene using a series of related PCP pincer palladium(II) complexes was studied in order to evaluate the effect of ligand structure and electronics on the catalytic activity and to investigate the nature of the catalyst species. We suggest these pincer complexes are precatalysts for highly active forms of metallic palladium. This conclusion is based on kinetic studies (induction periods, sigmoidal kinetics), Hg drop tests, quantitative poisoning experiments, and NMR studies.

show abstract

mentioning

confidence: 53%

Insights into the Heck Reaction with PCP Pincer Palladium(II) Complexes

2004

View full text Add to dashboard Cite

show abstract

“…Solutions of 6b heated in the presence of Cs 2 CO 3 , or a mixture of Cs 2 CO 3 and Hg, however, became yellow colored and gave new species as indicated by the presence of new 31 P NMR signals (62.2 and 52.6 ppm, respectively). These new resonances might suggest the presence of i Pr 2 P(=O)OAr functionalities and oxidation of the ligand system in 6b . One of several possible transformations of palladium phosphinite ligands involves hydrolysis .…”

Section: Resultsmentioning

confidence: 92%

“…. These new resonances might suggest the presence of i Pr 2 P()O)OAr functionalities 72 and oxidation of the ligand system in 6b. One of several possible transformations of palladium phosphinite ligands involves hydrolysis.…”

Section: Table 3 Suzuki-miyaura CC Coupling Reactions Between Substit...mentioning

confidence: 91%

m-Terphenyl Anchored Palladium Diphosphinite PCP-Pincer Complexes That Promote the Suzuki−Miyaura Reaction Under Mild Conditions

et al. 2008

View full text Add to dashboard Cite

Diphosphinite PCP-pincer pro-ligands anchored by a meta-terphenyl backbone were synthesized. These pro-ligands, [2,6-(2-Ph2POC6H4)2C6H3X] (3a X = I, 3b X = Br) and [2,6-(2- i Pr2POC6H4)2C6H3X] (4a X = I, 4b X = Br) upon reaction with Pd2(dba)3 yield PCP palladium pincer complexes [2,6-(2-Ph2POC6H4)2C6H3PdX] (5a X = I, 5b X = Br) and [2,6-(2- i Pr2POC6H4)2C6H3PdX] (6a X = I, 6b X = Br). The structures of 5a−b and 6a−b were determined by single crystal X-ray diffraction analyses. Complexes 5b and 6b were evaluated for their efficacy in promoting catalytic Suzuki−Miyaura CC coupling reactions. A variety of aryl bromides efficiently underwent CC coupling reactions with p-tolylboronic acid with high yields in the presence of either 5b or 6b. Compound 6b also proved to be a very active pro-catalyst for the coupling of aryl chlorides with p-tolylboronic acid. Excellent to good yields (in some cases greater than 90%) were achieved even with electron rich or sterically hindered aryl chlorides.

show abstract

“…Predominant conformation of the 1-alkoxy-3-methyl-hexahydrophosphinine oxides (29) was evaluated on the basis of stereospecific 3 J(P,C) coupling constants detected on the skeletal methyl group of the molecules. The Karplus equation was again a useful tool in the conformational analysis [22,23].…”

Section: Saturated Derivatives From 12-dihydrophosphinine Oxidesmentioning

confidence: 99%

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Keglevich

2006

COC

View full text Add to dashboard Cite

The members of a logically built P-heterocyclic family are discussed systematically to show a dynamically developing discipline of organophosphorus chemistry. Dichlorocyclopropanation of 2,5-dihydro-1H-phosphole oxides led to 3-phosphabicyclo[3.1.0]hexane 3-oxides that were useful intermediates for the synthesis of ring expanded products, such as 1,2-dihydrophosphinine oxides and 3-alkoxy-1,2,3,6-tetrahydrophosphinine oxides. Catalytic hydrogenation of 1,2-dihydrophosphinine oxides gave 1,2,3,4,5,6-hexahydrophosphinine oxides. Selective reduction of the , -doublebond of 1,2-dihydrophosphinine oxides via hydroboration led to 1,2,3,6-tetrahydrophosphinine oxides. Michael addition of >P(O)H species to the electron-poor double-bond of 1,2-dihydrophosphinine oxides afforded 1,2,3,6-tetrahydrophosphinine oxides with exocyclic P-function in position 3. Hydrogenation of these P-heterocycles led to the corresponding hexahydrophosphinine oxides. Stereostructure and conformation of the tetra-and hexahydrophosphinine oxides were elucidated by stereospecific NMR couplings and/or quantum chemical calculations. After deoxygenation, some of the above P-heterocycles were suitable P-ligands in transition metal complexes. The 1,2-dihydrophosphinine oxides were also useful in the synthesis of aromatic phosphinines, phosphepine derivatives and phosphabicyclo[2.2.2]octene oxides, as well as hetrocyclic -oxophosphoranes.

show abstract

Formation of aryl dialkylphosphinates from dialkylphosphinous chlorides and arylmagnesium bromides under oxidative conditions

Cited by 3 publications

References 0 publications

Insights into the Heck Reaction with PCP Pincer Palladium(II) Complexes

Insights into the Heck Reaction with PCP Pincer Palladium(II) Complexes

m-Terphenyl Anchored Palladium Diphosphinite PCP-Pincer Complexes That Promote the Suzuki−Miyaura Reaction Under Mild Conditions

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Contact Info

Product

Resources

About