Hydrostannylation of Red Phosphorus: A Convenient Route to Monophosphines

Abstract

The preparation of valuable and industrially relevant organophosphorus compounds currently depends on indirect multistep procedures involving difficult‐to‐handle white phosphorus as a common P atom source. Herein, we report a practical and versatile method for the synthesis of a variety of monophosphorus compounds directly from the bench‐stable allotrope red phosphorus (Pred). The relatively inert Pred was productively functionalised by using the cheap and readily available radical reagent tri‐n‐butyltin hydride, and subsequent treatment with electrophiles yields useful P1 compounds. Remarkably, these transformations require only modest inert‐atmosphere techniques and use only reagents that are inexpensive and commercially available, making this a convenient and practical methodology accessible in most laboratory settings.

Photochemical Benzylation of White Phosphorus

“…Quaternary phosphonium salts can be used as a tool for organic synthesis, ionic liquids, phase transfer catalysts, anticancer drugs, anti-microbial agents, and so on . Recently, chlorine-free methods of tetrabenzylphosphonium salts have been developed by converting P 4 into (Bu 3 Sn) x PH 3– x ( x = 1–3) intermediates, which then reacted with benzyl bromide, or using the reaction of [P­(SiCl 3 ) 2 ] − with benzyl chloride (Scheme a) . The tetrabenzylphosphonium salts can be used instead of the benzyltriphenylphosphonium salts in the Wittig reaction, which was a common Wittig reagent for converting benzaldehyde to styrene derivatives (Scheme b) .…”

“…From the economic and waste-disposal viewpoints, the direct functionalization of P 4 without chlorination to construct P–C bonds is of great significance and is becoming a hot area . There are some methods to achieve P 4 activation, − but the strategy for the direct construction of P–C bonds is still very limited. − Currently, many recent studies have witnessed the rapid development of photochemistry in the field of synthetic organic chemistry; however, photochemistry is rarely used in the synthesis of OPCs through the direct formation of P–C bonds from P 4 . The direct construction of P–C bonds by photoactivation of P 4 can be divided into two ways (Scheme a).…”

Direct and Rapid Synthesis of Arylphosphines (PIII) by Oxalyl Chloride Promoted Reduction of Inorganic Phosphorus Salts [TBA][H2PO4] with Trichlorosilane and Palladium Catalysis

“…Among those, the most well-known and practical route is the transformation of P 4 allotrope into PCl 3 , involving toxic and oxidizing Cl 2 gas with the drawbacks aforementioned. Although exhaustive efforts have been contributed to the investigation of effective, environmentally benign, and affordable routes for the synthesis of OPCs with small organophosphorus complexes (P 1 molecules) 1,30,39,40,41 , the use of inorganic phosphorus salts as precursors, which have advantages of wide availability and the avoidance of the extra transformation steps to either PCl 3 /PH 3 or their organic counterparts, has been much less investigated in this aspect, presumably due to the issues with reactivity, complexity, and productivity of the substrate in the past.…”