1067-73-8Relevant articles and documents
Reaction of Diethyl Phosphorochloridite with Enolates: A General Method for Synthesis of β-Keto Phosphonates and α-Phosphono Esters through C-P Bond Formation
Lee, Koo,Wiemer, David F.
, p. 5556 - 5560 (1991)
The reaction of ketone enolates with diethyl phosphorochloridite, followed by air oxidation of the intermediate reaction products, has proven to be a general and convenient method for preparation of β-keto phosphonates.Fourteen β-keto phosphonates have been prepared by this method, in an average yield greater than 60percent.This procedure also appears to be applicable to preparation of both α-phosphono aldehydes and α-phosphono esters.Although special precautions may be necessary to avoid aldol condensation during formation of aldehyde enolates, in two cases it was shown that the resulting enolates react readily with diethyl chlorophosphite.Finally, a set of five ethyl esters was converted to α-phosphono esters by this method.Yields of the α-phosphono esters are influenced by steric hindrance at the enolate carbon, but the average yield for this series was ca. 70percent.Because this synthetic method relies upon an electrophilic phosphorus reagent for formation of the C-P bond, it is complementary to the traditional Arbuzov synthesis.On the basis of the 21 examples presented here, it appears to be more widely applicable.
A new synthesis of 2-aryl-2-oxoalkylphosphonates from triethyl phosphonoacetate
Kim,Kong,Rhie
, p. 2865 - 2869 (1995)
Acylation of triethyl phosphonoacetate using magnesium ethoxide affords acyl phosphonoacetates which, on treatment with catalytic p-TsOH in water, are converted into 2-aryl-2-oxoalkylphosphonates.
Silver-Catalyzed Oxidative C(sp3)?P Bond Formation through C?C and P?H Bond Cleavage
Li, Lili,Huang, Wenbin,Chen, Lijin,Dong, Jiaxing,Ma, Xuebing,Peng, Yungui
supporting information, p. 10539 - 10544 (2017/08/22)
The silver-catalyzed oxidative C(sp3)?H/P?H cross-coupling of 1,3-dicarbonyl compounds with H-phosphonates, followed by a chemo- and regioselective C(sp3)?C(CO) bond-cleavage step, provided heavily functionalized β-ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional-group tolerance, and exclusive selectivity.
Addition of secondary amines to alkynylphosphonates
Panarina, Anna E.,Dogadina, Alla V.,Zakharov, Valentin I.,Ionin, Boris I.
, p. 4365 - 4368 (2007/10/03)
Addition of secondary amines to alkynylphosphonates catalyzed by Cu(I) salts proceeds regio- and stereospecifically to form (E)-2-(dialkylamino)alkenylphosphonates. The E-configuration was proved by analysis of 13C-31P vicinal spin-spin coupling constants in the NMR spectra of the products and authentic model compounds. The 3JPC constants in the model compounds fall in the range of 6-12 Hz for the cis arrangement of the coupled nuclei and are equal to or higher than 16 Hz for the trans configuration. Related coupling constants in the addition products are around 5 Hz, that is, corresponding to cis coupling.