Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P-C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving initial oxidation of white phosphorus (P 4 ) with hazardous chlorine gas and the subsequent displacement of chloride ions. Catalytic P 4 organofunctionalisation reactions have remained elusive, as they require multiple P-P bond breaking and P-C bond formation events to break down the P 4 core, all of which must occur in a controlled manner. Herein, we describe an efficient transition metalcatalyzed process capable of forming P-C bonds from P 4 . Using blue light photocatalysis, this method directly affords valuable triarylphosphines and tetraarylphosphonium salts in a single reaction step.The academic, industrial and societal importance of phosphorus chemistry is difficult to overstate. Phosphorus is one of the six essential 'biogenic elements' required in large quantities by every living organism, and synthetic phosphorus compounds find myriad industrial and commercial applications due to their diverse array of useful chemical, physical and biological properties. 1 This importance is reflected in the fact that white phosphorus (P 4 ) is currently produced on an estimated scale of >1 Mt / year. 2 P 4 is by far the most reactive and industrially-relevant form of elemental phosphorus, and acts as the common precursor from which effectively all synthetic phosphorus-containing species are ultimately Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:

Detailed 31 P{ 1 H} NMR spectroscopic investigations provided eeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P 4 ). Specifically,t hese studies have identified anumber of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et 3 N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy) 2 ][PF 6 ]( dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) and 3DPAFIPN.I nspired by the observation of PH 3 as am inor intermediate,w eh ave developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P 4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.

Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compoundso ften demande ither harsh reaction conditions, prefunctionalization of startingm aterials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methodst husr emain elusive, despite being of great current interest. Herein, we describe av isible-light-drivenm ethod to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated anda rylatedu sing commercially available organohalides.I na ddition, the sameo rganocatalyst can be used to transform white phosphorus(P 4)d irectly into symmetrical aryl phosphines and phosphonium salts in as ingle reaction step, whichh as previously only been possibleu sing precious metalc atalysis.

Abstract Recent advances in the development of coupled photoredox systems for the oxygenation of organic compounds are reviewed.

Detailed 31 P{ 1 H} NMR spectroscopic investigations provided eeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P 4 ). Specifically,t hese studies have identified anumber of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et 3 N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy) 2 ][PF 6 ]( dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) and 3DPAFIPN.I nspired by the observation of PH 3 as am inor intermediate,w eh ave developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P 4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.

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