Jingyuan Hu

Bio: Jingyuan Hu is an academic researcher from Peking University. The author has contributed to research in topics: White Phosphorus. The author has co-authored 1 publications.

Recent Breakthroughs in P4 Chemistry: Towards Practical, Direct Transformations into P1 Compounds

Abstract: Abstract For several decades, academic researchers have been intensively studying the chemistry of white phosphorus (P4) in the hope of developing direct methods for its transformation into useful P‐containing products. This would bypass the hazardous, multistep procedures currently relied on by industry. However, while academically interesting P4 activation reactions have become well established, their elaboration into useful, general synthetic procedures has remained out of reach. Very recently, however, a series of independent reports has begun to change this state of affairs. Each shows how relatively simple and practical synthetic methods can be used to access academically or industrially relevant P1 compounds from P4 directly, in “one pot” or even in a catalytic fashion. These reports mark a step change in the field of P4 chemistry, and suggest its possible transition from an area of largely academic interest to one with the promise of true synthetic relevance.

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition-Metal- and Photocatalyst-Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus.

Abstract: Developing practical and mild strategies for the direct functionalization of white phosphorus (P 4 ) without chlorination is an appealing but formidable challenge. Toward this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon-centered radicals from N -hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P 4 molecule under transition-metal- and photocatalyst-free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one-pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct P-F, P-C, P-N and, P-O bonds was also demonstrated.

Recent Breakthroughs in P ₄ Chemistry: Towards Practical, Direct Transformations into P ₁ Compounds

Abstract: For several decades, academic researchers have been intensively studying the chemistry of white phosphorus (P4) in the hope of developing direct methods for its transformation into useful P-containing products. This would bypass the hazardous, multistep procedures currently relied on by industry. However, while academically interesting P4 activation reactions have become well established, their elaboration into useful, general synthetic procedures has remained out of reach. Very recently, however, a series of independent reports has begun to change this state of affairs. Each shows how relatively simple and practical synthetic methods can be used to access academically or industrially relevant P1 compounds from P4 directly, in “one pot” or even in a catalytic fashion. These reports mark a step change in the field of P4 chemistry, and suggest its possible transition from an area of largely academic interest to one with the promise of true synthetic relevance.

Direct Synthesis of Dialkylphosphites from White Phosphorus

Abstract: Dialkyl phosphites (DAPIs), traditionally prepared from hazardous and corrosive PCl3, are the fundamental reactive starting materials used in organophosphorus chemistry. Here, a KBr-mediated synthesis of DAPIs involving P4, alcohols and water is presented. With the use of silica gel as the catalyst, oxone as the safe oxidant, industrially important (EtO)2P(O)H, (i-PrO)2P(O)H and (MeO)2P(O)H are prepared in 70–90% yields. Furthermore, rare metal extractant bis(2-ethylhexyl) phosphate (D2EHPA) is obtained in 73% yield. The reaction is characterized by a complete conversion of white phosphorus. Moreover, this method can be easily adapted to large-scale preparation.