Nature of acid-catalyzed alcoholysis of amides of trivalent-phosphorus acids

Derivatives of trivalent phosphorus in the synthesis of glycerophosphatides and related phospholipids

“…This silyl phosphite was converted by oxidation (by the addition of oxygen, sulfur, and selenium) into the COC1 18 According to 31 P NMR data, thio-and seleno-phosphatidic acids exist in chloroform solutions in the thiono-and selenonophosphoryl forms. A similar conclusion concerning the structure of the seleno-acids was also reached from analysis of the direct 77 Se -31 P spin -spin coupling constants.…”

N‐Phosphanylformamidines (phosfam) R2′N–C(H)=N–PR2: One‐Pot Synthesis and Versatile Protonation Reaction

“…[8] Protonation reactions with preservation of the phosphorus-nitrogen linkage are believed to take place initially at the P-center. P-protonated phosphorus amides [9] as well ergetically close, which prevents conclusions being drawn on the existence of thermodynamic and/or kinetic products. The accessibility of the anti bonding PN orbital (σ* P1N1 ) is partly responsible for the cleavage of the PN bond in 8a; 8b possesses a less energetically accessible σ* P1N1 orbital which is consistent with the preservation of the PN bond and the quantitative formation of the corresponding phosphonium compound 9b·Cl.…”

“…To the best of our knowledge, an N-protonated isomer of a P III -N amide unit has never been detected except when treating tetramethylguanidinyl P III amides with HCl. [11] If we refer to the results described in the literature on the protonation of aminophosphanes ϾP-NϽ [9][10] and (methyleneamino)phosphanes ϾP-N=CϽ [11] it is not possible to anticipate the privileged site of protonation of N-phosphanylformamidines 3a,b and the thermodynamic stability of the corresponding protonated compounds.…”

A Versatile Protocol for the Quantitative and Smooth Conversion of Phosphane Oxides into Synthetically Useful Pyrazolylphosphonium Salts

“…[20] In cation 3a + (Figure 1) the coordination sphere at the phosphorus atom possesses almost ideal tetrahedral geometry (angles span 108.2(9)-111.2(1)8). The PÀN bond length (1.683 (2) ) is in the typical range of P(tetravalent)À N(sp 2 ) bonds if the P atom is tetravalent (e.g., [(PMe 3 ) 2 NH] 2 + 1.655 and 1.661 ; [22] [tBu 2 P(H)pyrrole] + 1.669 ; [23] Ph 2 P-(BH 3 )pyrrole 1.711 ; [24] and [PMe 3 DMAP] 2 + , DMAP = 4-dimethylaminopyridine, 1.720 [25] ) and does not significantly depend on the substituents on phosphorus (compare 3c + and 3e + ; Figure 1; see the Supporting Information for further details and natural bond orbital analysis of 3a + ). We extended our approach to a series of phosphane oxides (Scheme 3).…”