The Structure and Properties of the Dialkyl Phosphonates.

Doak, G. O.; Freedman, Leon D.

doi:10.1021/cr60209a002

Cited by 99 publications

(39 citation statements)

References 37 publications

(47 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Instead, the majority of reports focus on the coupling of H -phosphonates with various partners in a C-P bond forming process. H -Phosphonates are known to exhibit tautomeric behavior between the favored phosphonate form and the more nucleophilic phosphite, 1146 which in turn participates in these oxidative couplings. 1147 In the context of copper-oxygen catalysis, however, oxidation at phosphorus is concomitant with carbon-phosphorus bond formation.…”

Section: Oxidation Of Phosphorus Compoundsmentioning

confidence: 99%

Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

View full text Add to dashboard Cite

24 peroxide [Cu I (pyr)(tpb)] 10 mol % TBHP, 1 atm O 2 , 1:2 AcOH/pyr, rt, 24 h ∼2.5 26 74 g 35 25 n-hexane aldehyde CuCl 2 , 18-crown-6 1 atm O 2 , MeCHO, CH 2 Cl 2 , 70 °C, 24 h 2.4 91 h 9 34a 26 n-decane aldehyde Cu II Cl 16 Pc-AM(PS) 3 equiv of PhCHO, MeCN, 1 atm O 2 , 50 °C 15.4 100 i 61 a See Chart 2 for ligand structures. b Also 28% cyclohexene. c Also 26% cyclohexene. d Mixture of alcohol and hydroperoxide. e Remainder of product is cyclohexene. f Approximately 93:7 of 1-adamantol/2-adamantol. g Approximately 98:2 of 1-adamantol/2-adamantol. h Afforded oxidation products in an approximately 1:1 ratio at the 2-and 3-positions. i Mixture of decanones.

show abstract

Section: Oxidation Of Phosphorus Compoundsmentioning

confidence: 99%

Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

View full text Add to dashboard Cite

show abstract

“…As tetravalent dialkyl H-phosphonates HP(O)(OR) 2 are in equilibrium with their dialkyl phosphite tautomers P(OH)(OR) 2 , [2,44,45] the formation of the carbon-phosphorus bond can be explained by the reaction of the iminium ion with P(OH)(OR) 2 .…”

Section: Mechanismmentioning

confidence: 99%

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

2010

View full text Add to dashboard Cite

Abstract:The dehydrogenative a-phosphonation of substituted N,N-dialkylanilines by dialkyl H-phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert-butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron-donating (methoxy, methyl, benzyl) and electron-withdrawing ring-substitutents (bromo, carbonyl, carboxyl, m-nitro) in moderate to good yields. The X-ray crystal structure of N-(5,5-dimethyl-2-oxo-2l 5 -[1,3,2]dioxaphosphinan-2-yl-methyl)-N-methyl-p-toluidine was determined. Bis-(4-(dimethylamino)phenyl)methane and bis-4,4'-(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess di-

show abstract

“…For different systems, for example various amines or solvents, rate constants will change according to the equations (12)or (13).…”

Section: Methodsmentioning

confidence: 99%

On the Nature of the Nucleophile in the Mixture of Phosphites and Amines

Gancarz

2000

Phosphorus, Sulfur, and Silicon and the Related Elements

View full text Add to dashboard Cite

It is now commonly accepted that in the presence of strong bases (like metal alcoholates) an equilibrium between phosphite and phosphonate forms of dialkyl phosphites exists and that the phosphite form is highly reactive in the reaction with carhonyl compounds. There is a controversy on the structure of the active form of the phosphite when the addition is catalyzed by amines. We have found that aliphatic amines and dialkyl phoshites form a complex which is a reactive species. Its stoichiometry depends on the nature of the solvent.

show abstract

The Structure and Properties of the Dialkyl Phosphonates.

Cited by 99 publications

References 37 publications

Aerobic Copper-Catalyzed Organic Reactions

Aerobic Copper-Catalyzed Organic Reactions

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

On the Nature of the Nucleophile in the Mixture of Phosphites and Amines

Contact Info

Product

Resources

About