First examples of methylene insertion into the phosphorus(III)–nitrogen bond

PN Bond Cleavage during the Insertion of Carbon Fragments into PIIIN Bonds in Bis(diphenylphosphino) Amines

“…The insertion reactions are driven by the formation of thermodynamically stable P¼O bonds similar to other P-based reactions such as Wittig, Michaelis, Arbuzov, and Mitsunobo reactions [15]. As a part of our interest on bis(phosphino)amines, we report herein, after Priya et al [12], the second observed insertion reactions of the bis(phosphino)amines 1a -1c with several aldehydes to furnish the inserted products.…”

“…In their first study on insertion [12], Priya et al asserted that the mechanism of the insertion reaction follows the StaudingerÀWittig pathway, which involves H-atom transfer from the N-to P-atom, leading to the intermediate Ph 2 P(O)H. However, they then realized that this mechanism failed to explain the insertion observed in non-H-containing phosphinoamines such as RN(PPh 2 ) 2 and Ph 2 PN(C 2 H 4 ) 2 NPPh. Therefore, they concluded that the presence of the NH group was not necessary for the insertion reactions and proposed another tentative mechanism for the insertion reactions involving a phosphaoxirane intermediate.…”

“…Furthermore, these compounds can be reacted with P III reagents to obtain heterodifunctional ligands containing soft P-and hard O-donor centers, which can serve as potential bonding sites of metals in homogeneous catalysis in organic synthesis [12] [22].…”

“…However, insertion of aldehydes into PÀN bonds is not a common reaction in chemical processes. Recently, Priya et al reported the first insertion of C-fragments into PÀN bonds in the reaction of phosphino-amines with aldehydes, which led to the formation of a-amino phosphonates [12].The P …”

Synthesis, characterization and the crystal structures of novel achiral and chiral α-ferrocenyl α-aminophosphine oxides

“…Starting from a-aminoacids, some a-aminophosphine oxides were also synthesized as potential HIV-Protease Inhibitors [2]. Recently, Balakrishna et al found that reactions of Ph 2 PN(H)Ph with paraformaldehyde or aromatic aldehydes led to the insertion of 'RCH' into the P(III)AN bond to give a-aminophosphine oxides Ph 2 P(O)CH(R)N(H)Ph (R=H, Ar) and they studied the coordination properties of Ph 2 P(O)CH 2 N(H)Ph with Zn, Cd, Hg and U [3][4][5]. In addition, aminophosphine oxides are found to be useful ligands in some catalytic reactions.…”