Fragmentation-Related Phosphonylation of Nucleophiles Utilizing P-Alkyl 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide Precursors

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source

“…have generated considerable scientific interest due to their potential as phosphorylation/phosphonylation reagents − as well as their participation as intermediates/final products of combustion reactions involving warfare agents and flame retardants. , Dioxyphosphorane ( 1 , Figure ) and cis / trans -alkoxyphosphanone ( 2 , 3 ) are the structural isomers that these molecules are capable of adopting. The former, formally a P­(V) species, is thermodynamically more favorable for all species regardless of the nature of the R substituent − ,− with the exception of the parent compound (i.e., R = H). − In fact, parent dioxophosphorane 1a has been predicted to be more than 40 kJ/mol less stable than the cis-isomer of hydroxyphosphanone ( 2a ), − and it was then not surprising that this least thermodynamically stable isomer (i.e., HPO 2 ) was only recently detected via infrared spectroscopy among several products formed during 193/266 nm laser photolysis of 2a in the Ar matrix at 2.8 K …”

Probing the Structural and Electronic Effects on the Origin of π-Facial Stereoselectivity in 1-Methylphosphole 1-Oxide Cycloadditions and Cyclodimerization

“…The Diels–Alder reactions of P­(IV) derivatives of phosphole have attracted the attention of experimental and computational chemists because such reactions form a 7-phosphanorbornene moiety that holds unique properties of its P-center. − The significance of the 7-phosphanorbornene derivatives was explained by Quin, Mathey et al, in fragmentation-related phosphorylation reactions, , complexations, − and in refunctionalization − including deoxygenations. − Westheimer first reported the preparation of P­(IV) derivatives of phosphole, which was further explored for the synthesis of the dimers of phosphole derivatives including oxides, sulfides, and quaternary salts. − …”

Synthesis of 1,2-oxaphosphinane 2-oxides and 1,2-oxaphosphinine 2-oxides: δ-phosphonolactones and δ-phosphinolactones

“…The oxidation also gave the regiomeric oxidation products with poor regioselectivity, oxygen insertion in less steric C-P side as the major process (Scheme 76). [109][110][111] 3-Alkyl-2,3-oxaphosphabicyclo[2.2.2]octane 3-oxides can be applied as phosphonylating reagents as well because they generate alkylmetaphosphonates, which are phosphorus analogues of the acyl group, under heating. [109][110][111] Although the Baeyer-Villiger oxidation can convert 7-phosphanorbene 7-oxide derivatives to the corresponding 2,3oxaphosphabicyclo[2.2.2]octane 3-oxides, the oxidation generally gave the desired products in low yield with low regioselectivities for unsymmetric reactants, even needing long reaction time in some cases.…”

“…The oxidation also gave the regiomeric oxidation products with poor regioselectivity, oxygen insertion in less steric C–P side as the major process (Scheme 76). 109–111 3-Alkyl-2,3-oxaphosphabicyclo[2.2.2]octane 3-oxides can be applied as phosphonylating reagents as well because they generate alkylmetaphosphonates, which are phosphorus analogues of the acyl group, under heating. 109–111…”