Direct visible-light-induced synthesis of P-stereogenic phosphine oxides under air conditions

Abstract

We describe a simple and efficient visible-light-induced C–P bond forming reaction for the synthesis of P-chiral heteroaryl phosphine oxides in moderate to high yields with excellent ee values (97–99% ee).

Recent advances in photochemical construction of aromatic C–P bonds via C–hetero bond cleavage

“…In 2022, this group developed a simple and efficient visible-light-induced aryl C–P bond formation of ( R )- tert -butyl(phenyl) phosphine oxide with heteroaryl chlorides, affording P -chiral heteroaryl phosphine oxides in moderate to high yields with excellent ee values (97–99% ee) (Scheme 12). 29 A variety of P -chiral heteroaryl phosphine oxides, including important chiral phosphine-containing ligands 11-11 and 11-12 , have been directly obtained under air conditions in the absence of transition-metal or photocatalysts. Based on the mechanistic studies and DFT calculations, a possible mechanism was proposed.…”

“…In 2022, this group developed a simple and efficient visiblelight-induced aryl C-P bond formation of (R)-tert-butyl( phenyl) phosphine oxide with heteroaryl chlorides, affording P-chiral heteroaryl phosphine oxides in moderate to high yields with excellent ee values (97-99% ee) (Scheme 12). 29…”

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

“…[32][33] A subsequent approach involves the direct functionalization of secondary phosphine oxides (SPO) by means of a metal catalyst bearing chiral ligands to obtain tertiary phosphine oxides. [34][35][36][37][38][39][40][41][42][43][44] To date, however, this approach has been largely limited to the synthesis of all carbon substituted phosphine oxides (Scheme 1B, iv). The final strategy is an enantioselective desymmetrization by which prochiral groups linked to a phosphorus center are differentiated by a chiral catalyst (Scheme 1B, v).…”

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

“…Thirdly, chiral, yet racemic at P(V) electrophiles bearing a single leaving group (and often possessing a chiral (single enantiomer) sidechain) can be coupled diastereoselectively to enantiopure nucleophiles employing chiral catalysts (Scheme 1B, iii) [32–33] . A subsequent approach involves the direct functionalization of secondary phosphine oxides (SPO) by means of a metal catalyst bearing chiral ligands to obtain tertiary phosphine oxides [34–44] . To date, however, this approach has been largely limited to the synthesis of all carbon substituted phosphine oxides (Scheme 1B, iv).…”