Organophosphorus compounds have long been considered valuable in both organic synthesis and life science. P(III)-nucleophiles, such as phosphites, phosphonites, and diaryl/alkyl phosphines, are particularly noteworthy as phosphorylation reagents for their ability to form new P-C bonds, producing more stable, ecofriendly, and cost-effective organophosphorus compounds. These nucleophiles follow similar phosphorylation routes as in the functionalization of P-H bonds and P-OH bonds. Activation can occur through photocatalytic, electrocatalytic, or thermo-driven reactions, often in coordination with a Michaelis-Arbuzov-trpe rearrangement process, to produce the desired products. As such, this review offers a thorough overview of the phosphorylated transformation and potential mechanisms of P(III)-nucleophiles, specifically focusing on developments since 2010. Notably, this review may provide researchers with valuable insights into designing and synthesizing functionalized organophosphorus compounds from P(III)-nucleophiles, guiding future advancements in both research and practical applications.

The immobilization of enzyme on solid supports as the heterogeneous catalyst is an efficient strategy to enhance the catalytic performance and reusability. MOFs supports show huge potential for enzyme immobilization, however, suffer from poor stability thus reducing the effective loading of enzyme and resulting in low catalytic performance. In this work, NH2-MOF-5 was synthesized and linked with the cross-linked PEI by chemical bond to form a novel composite support, the lipase PS was then immobilized onto the composite support through physical adsorption to synthesized PS@NH2-MOF-5@PEI in hexane. Benefitting from the stable nano-flower structure and strong adsorption for lipase PS of the NH2-MOF-5@PEI, the synthesized PS@NH2-MOF-5@PEI showed huge specific surface area (only decreased 5.90 % after immobilization) and enhanced alpha-helix and beta-turn (increased 29.80 % and 52.88 %, respectively), thus exhibiting excellent catalytic activity which was about 2 times higher than that of free lipase PS, as well as outstanding recyclability after 8 cycles. We believe the strategy of immobilization of enzymes on a novel NH2-MOF-5@PEI support will exhibit huge potential of biocatalyst for further application.

The functionalized heterogeneous Cu-chitosan based catalyst was developed for the regioselective hydrophosphorylation of alkynes with secondary H-phosphine oxides. The functionalized chitosan framework was produced through a cross-coupling reaction between chitosan and 2,4,6-trichloro-1,3,5-triazine. Following this, the coordination of Cu(OAc)2 with the functionalized chitosan framework led to the synthesis of the heterogeneous Cu-chitosan based catalyst. Various techniques, such as powder FT-IR spectroscopy, X-ray diffraction (XRD), N2 physical adsorption, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), were employed to characterize the catalyst. Subsequently, the resulting Cu(OAc)2@chitosan@2,4,6-trichloro-1,3,5-triazine catalyst exhibited remarkable catalytic activity in the regioselective hydrophosphorylation of alkynes with the formation of P–C bonds, displaying exceptional E/Z selectivity. This successful catalysis led to the synthesis of a range of (E) anti-Markovnikov adducts with high yields. The catalyst shows high recyclability in this transformation. On the basis of step-by-step control experiments, a plausible mechanism is proposed.

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis-Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)(3), ArP(OR)(2), and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and P-31 NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation.

A simple and efficient method for the synthesis of diarylmethyl-functionalized anilines through the hexafluoroisopropanol (HFIP)-mediated regioselective 1,6-hydroarylation reaction of para-quinone methides (p-QMs) with anilines under catalyst- and additive-free conditions is reported. Various kinds of p-QMs and amines (e. g. primary, secondary and tertiary amines) are well tolerated in this transformation without the pre-protection of amino group, and the corresponding products could be generated with good to excellent yields and satisfactory regioselectivity under the optimized reaction conditions. In addition to adaptable amine compounds, indoles and their derivatives are also compatible with this reaction system. This transformation can be easily extended to a gram scale-synthesis level to synthesize the target product. Furthermore, it is worth noting that some complex small aniline molecules with biological activity can be selectively modified using this method. The possible reaction mechanism is proposed through the step-by-step control experiments and DFT calculations, showing that the key process for achieving the regioselective 1,6-hydroarylation of p-QMs is the hydrogen bonding effect of HFIP to substrates.

In recent years, para-quinone methides (p-QMs) have been recognized as a series of electron-deficient alkenes due to their special conjugate structure, which are widely used as the diarylmethyl motif to synthesize natural products, functional materials, and organic intermediates in organic synthesis. Due to their special thermodynamic and chemical stability, para-quinone methides have emerged as a hot research topic. The construction of diarylmethyl substituted cyclic organic molecules through the intermolecular and intramolecular cyclization of p-QMs is particularly appealing. Thus, this review aims to systematically encapsulate the cyclization reactions and possible mechanisms of p-QMs that have been studied since 2017. This review will provide researchers with fresh ideas to design and synthesize novel p-QMs-derived structures for future applications.