Stereoselective synthesis of both enantiomers of P-chirogenic 2-oxo-2-thio-1,3,2-oxazaphosphorinane tetramethylammonium salt as key precursors to structurally diverse chiral derivatives

Mikołajczyk, M.; Łuczak, Jerzy; Sieroń, Lesław; Wieczorek, Michał W.

doi:10.1016/j.tet.2011.10.085

Cited by 4 publications

(1 citation statement)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…They also agree with the proposal, despite many overlapped signals as a result of the reaction medium (acetonitrile, tetrahydrofuran, H 2 O, and D 2 O, see the Supporting Information). At the end of the reaction, only two signals ( δ =8.20 and 7.27 ppm) could be observed in the aromatic region of the 1 H NMR spectrum, and according to the literature, they can be assigned to DMPT . Moreover, the signals of PNP ( δ =7.86 and 6.41 ppm) are clearly not present, which reaffirms that IMZ does not attack the phosphorus atom of IMZ.…”

Section: Resultssupporting

confidence: 64%

Puzzling Reaction of Imidazole with Methyl Parathion: P=S versus P=O Mechanistic Shift Dilemma in Organophosphates

Silva

Nascimento

Nunes

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

Organophosphates (OPs) constitute many toxic agrochemicals and warfare and can undergo a wide spectrum of mechanisms, some which are fairly unexplored. In this sense, concise mechanistic elucidation stands out as a strategic tool for achieving efficient detoxification and for monitoring processes. Particularly intriguing is the effect of substituting the oxygen atom of the phosphoryl moiety (P=O) in OPs with a sulfur atom to give the thio‐derived OPs (i.e., OTPs, P=S). In general, imidazole (IMZ) reacts very efficiently with OPs by targeting the phosphorus atom, although herein we evidence a thio‐driven shift with OTPs: IMZ undergoes unusual nucleophilic attack at the aliphatic carbon atom of methyl parathion. Alkylation of IMZ under mild conditions (aqueous weakly basic medium) is also novel and should be applicable to other novel IMZ‐based architectures, and thereby, it can be a great ally for organic synthesis. Overall, a broader understanding of the mechanistic trend involved in such highly toxic agents is provided.

show abstract

Section: Resultssupporting

confidence: 64%