2014-79-1Relevant academic research and scientific papers
Dealkoxylation ofN-alkoxyamides without an external reductant driven by Pd/Al cooperative catalysis
Suzuki, Hirotsugu,Shiomi, Takahiro,Yoneoka, Kenji,Matsuda, Takanori
, p. 7545 - 7548 (2020)
Lewis acid-assisted palladium-catalysed dealkoxylation ofN-alkoxyamides has been developed. This reaction proceeded smoothly with a range ofN-alkoxyamides in the absence of an external reductant, thereby establishing a convenient and reductant-free protocol. In addition, a gram-scale reaction could be achieved. Preliminary mechanistic investigations indicated that β-hydrogen elimination from a palladium alkoxide intermediate generated an intramolecular hydride source.
O -Phthalaldehyde catalyzed hydrolysis of organophosphinic amides and other P(O)-NH containing compounds
Li, Bin-Jie,Simard, Ryan D.,Beauchemin, André M.
supporting information, p. 8667 - 8670 (2017/08/10)
Over 50 years ago, Jencks and Gilchrist showed that formaldehyde catalyses the hydrolysis of phosphoramidate through electrophilic activation, induced by covalent attachment to its nitrogen atom. Given our interest in the use of aldehydes as catalysts, this work was revisited to identify a superior catalyst, o-phthalaldehyde, which facilitates hydrolyses of various organophosphorus compounds bearing P(O)-NH subunits under mild conditions. Interestingly, chemoselective hydrolysis of the P(O)-N bonds could be accomplished in the presence of P(O)-OR bonds.
Nucleophilic Substitution at the Tetracoordinated Phosphorus Atom. Reactivity of Amines towards Diphenyl Chlorophosphate in Acetonitrile
Solomoichenko,Sadovskii,Savelova,Piskunova,Popov
, p. 1434 - 1441 (2007/10/03)
Tertiary alkylamines, pyridines, and imidazoles catalyze the hydrolysis of diphenylchlorophosphate (acetonitrile, 25°C) by a nucleophilic mechanism with the rate-determining attack of an amine on the substrate. Primary and secondary alkyl and arylamines f
HYDROBORATION-OXIDATION OF 1-TRIALKYLSILYL DIALKYLPHOSPHORAMIDOPROPYNES REGIOSELECTIVITY AND REACTIVITY
Kerdel, Katia,Baboulene, Michel
, p. 39 - 54 (2007/10/02)
The regioselectivity of the hydroborationof 1-trialkylsilyl dialkylphosphoramidopropynes was studied.The directive role of silicon was not always observed.In some cases inductive effects of substituents led to different and event opposite regioselectivity.We found here an interaction between boron and the phosphoryl group for the C2 addition which has not previously been observed.After oxidation, this interaction leads to byproducts.Understanding of the scope and limitations of this hydroboration-oxidation reaction enabled selective synthesis of the novel phosphorylated acids and ketones.Key words: Silylated dialkylphosphoramidopropynes; hydroboration-oxidation; regioselectivity; reactivity.
Synthese et reactions de N-acylphosphoramides apparentes aux ceto-4 diaza-1,3 phospholanes-2
Mulliez, Michel
, p. 1211 - 1218 (2007/10/02)
A new, general method, more efficient than previous ones, for the synthesis of N-acylphosphoramides 3, by reacting the silylated primary phosphoramides 2 with carboxylic chlorides is described (Figure 2).It is applied to the synthesis of precursors B and C and acyclic analogs D and E of the 4-keto 1,3-diaza, 2-phospholanes A (Figure 1). 3c (B) and 3a (C) lead to 15 (A) (Figure 5) and 17 (Figure 6) (A) in presence of sodium hydride, and hydrogen with palladium on charcoal as catalyst, respectively.Phosphorane 19 is formed from 3a and triphenylphosphine (Figure 6).D and E are not phosphorylating reagents but acylating ones.
Phosphoric Amides. 7 - Mass Spectrometry of Phosphoric Amido Esters: Fragmentation Patterns and Migratory Aptitudes
Dawidowitz, Bette,Modro, Tomasz A.
, p. 128 - 134 (2007/10/02)
Mass spectra of 38 organophosphorus compounds, containing both phosphate ester (P(O)OR) and phosphoramidate (P(O)NR'R'') functional groups, were recorded and discussed.Attention was focused on P-N bond cleavage, which can involve simple fission, fission a
