Ternary Photoredox/Nickel/Halide Catalysis for the Phosphorylation of Alcohols with White Phosphorus

Abstract

Dialkyl phosphites (DAPIs) are important precursors in the formation of phosphorus−carbon and phosphorus− heteroatom bonds with significant industrial applications. Traditional PCl 3 -based procedures suffer from high waste production and toxic reaction conditions. The direct conversion of white phosphorus (P 4 ) to DAPIs can circumvent these issues by avoiding the use of Cl 2 and PCl 3 . We present a waste-free, environmentally friendly approach for synthesizing DAPIs using P 4 and alcohols, leveraging a combination of photoredox catalyst, nickel catalyst, and halide anion. This photocatalytic method enables the efficient coupling of various alcohols. Advantageously, this method is also suitable for the synthesis of trialkyl phosphates and triaryl phosphorotrithioates.

Sustainable Photo‐ and Electrochemical Transformation of White Phosphorous (P4) into P1 Organo‐Compounds

“…Very recently, Tang and co-workers developed a photoredox-catalyzed direct phosphorylation of alcohols with P 4 to access DAPIs and TAPAs through a synergistic catalysis of organic dye photocatalyst, nickel catalyst, and halide anion (Scheme 6). [30] The reaction generality testing demonstrated that a wide range of substituted alcohols bearing electronwithdrawing or sterically hindered groups are compatible with slightly modified conditions. The fluorescence quenching experiment on organic dye photocatalyst, Rhodamine-6G, observed an obvious fluorescence decline in a KI concentration-dependent manner, implying a SET behavior from the photoexcited state of Rhodamine-6G to halide anion.…”

“…As the expansion of former photo-phosphorylation of alcohols, thiophenols were amenable to the addition to P 4 to afford some phosphorotrithioate products (Scheme 7B). [30] While neither of the above work provides the explicit mechanism, it is speculated that the reaction occurred through the manipulation of sulfur-centered free radicals. However, the substrate scope is strictly restricted to thiophenols, whereas alkyl thiols cannot participate in the reaction.…”

Three-component coupling reaction of white phosphorus, alcohols and diaryl disulfides: a chlorine-free avenue for accessing phosphorothioates

“…[21][22][23][24][25] However, to the best of our knowledge, direct functionalization of P 4 for the synthesis of phosphorothioates has not been reported in the literature due to the challenge of cleaving all six P-P bonds of the P 4 tetrahedron and orderly installing different atoms at phosphorus center. [26][27][28][29][30][31][32] As a continuum of our efforts in developing green methodologies for the selective transformation of P 4 into useful P 1 products without hazardous chlorination steps, [33][34][35][36][37] we report the first copper-catalyzed three-component coupling reaction of P 4 , alcohols, and aryl disulfides for the synthesis of phosphorothioates under mild conditions, exhibiting high phosphorus conversion (Scheme 1e).…”

Construction of Phosphorothiolated 2-Pyrrolidinones via Photoredox/Copper-Catalyzed Cascade Radical Cyclization/Phosphorothiolation

“…Generally, methods for the synthesis of organophosphorothioates mainly rely on the formation of the P–S or C–S bonds through substitution reactions, cross-coupling reactions, and radical-based reactions . In recent years, Ir or Cu catalysts showed their uniqueness in chemical bond activation and were proven to be successful for realizing various challenging chemical reactions .…”