Although more advantageous in several aspects than the reaction of the corresponding halides, the catalytic Michaelis-Arbuzov (MA) reaction of sterically more bulky secondary and tertiary alcohols with triorganyl phosphites is still one of the most challenging tasks that has not been realized so far. Now we have developed a trimethylsilyl triflate (TMSOTf)-catalyzed efficient MA reaction of triorganyl phosphites that can directly employ sterically bulky alcohols as substrates. This new method can be applied to a wide range of primary to tertiary alcohols and also two P(III) esters (phosphonites and phosphinites), providing a general, practical, green and advantageous catalytic MA reaction for the preparation of useful organophosphoryl compounds including phosphonates, phosphinates, and phosphine oxides. Control reactions and density functional theory (DFT) calculations of the reaction revealed that the mechanism of this new MA reaction may be rather complicated: an initial step-wise activation of the substrates to the more reactive intermediates, followed by two different catalytic cycles involving both the SN1 and SN2 processes may be involved in the reaction mechanism.

Thiophenols/thiols are important building blocks for the synthesis of a variety of pharmaceutically important sul-fur-containing compounds.Due to the versatile functionalities in organic synthesis,herein,the development of thiols synthesis via rhodium-catalyzed hydrogenation of RS-SR was reported.Green and clean hydrogen is used as the reductant.This trans-formation exhibits excellent functional group tolerance,a wide range of aryl or alkyl disulfides were reduced to the corre-sponding thiols in good to excellent yields with a loading of rhodium catalysts down to 0.05 mol％.This reaction also can be carried out at a large gram scale.And the catalysts can be recycled three times without diminishing the catalytic activity.All of these show that this method for hydrogenation of disulfide has great potential for industrial production.

ABSTRACT An unprecedented P–S coupling of trifluoroacetophenone N ‐sulfonylhydrazones with diarylphosphine oxides is described to afford phosphorothioates with high selectivity. In contrast to the conventional use of N ‐sulfonylhydrazones as diazo precursors, trifluoroacetophenone‐derived N ‐sulfonylhydrazones formally transfers a RS moiety in the reaction. The reaction scope was examined and a plausible mechanism proposed based on control experiments.

A zinc-catalyzed method has been developed for the direct conversion of primary alcohols into alkenes under acceptorless dehydrogenation conditions. Utilizing a simple and Earth-abundant zinc catalyst, this approach enables the dehydrogenative coupling of primary alcohols with either diphenylphosphine oxide (to generate symmetric alkenes) or benzyl phosphine oxides (to generate asymmetric alkenes), affording a diverse range of alkenes in moderate to high yields with (E)-selectivity. This strategy provides a promising facile route for alkene synthesis directly from readily accessible alcohols, as evidenced by gram-scale reactions and the preparation of the biologically active compounds DMU-212 and resveratrol.

Different to other solvents, a unique promoting effect of DMF is observed in the aromatic nucleophilic substitution reaction of heteroaryl halides and thiols. Thus, by using DMF as the solvent, a greener method can be developed for direct neutral synthesis of heteroaryl thioethers without adding any external base into the reaction. This method can also be extended to alkyl and electron-deficient aryl halides, providing a new way for external base-free neutral construction of the useful unsymmetrical thioethers. Control reactions revealed that DMF functions more than a good solvent in the reaction, i.e., a synergetic bifunctional effect of DMF working as both the best solvent and an excellent organic base can eventually promote the substitution reactions of thiols and organohalides effectively without using any external base.

We report a novel metal-free method for selectively reducing aromatic alkynes and alkenes by using phosphonic acid. When combined with molecular iodine, this system reduces aromatic alkynes to the corresponding (E)-alkenes and alkanes in high yields. Additionally, various aromatic alkenes can be directly reduced with comparable efficiency. This protocol features low cost, simple conditions, and the avoidance of metal catalysts.

Triphenylphosphine oxide and pyrophosphonic acid are two phosphorus-containing industrial wastes generated in tens of thousands of tonnes annually. Currently, the former is partially recycled using toxic phosgene, while the latter is mostly discarded. Here we report an unprecedented catalytic reaction that simultaneously upcycles both wastes. We found that simply heating a mixture of triphenylphosphine oxide and pyrophosphonic acid with a catalytic amount of a common iodo compound (e.g., NaI or CH2I2) efficiently reduces triphenylphosphine oxide to valuable triphenylphosphine, while converting pyrophosphonic acid to phosphoric acid. This one-pot, operationally simple process is economically viable for industrial-scale transformation. Mechanistic studies reveal that pyrophosphonic acid activates the strong P=O bond of triphenylphosphine oxide via an anhydride-type interaction, enabling reduction by the iodine catalyst. Our “two birds with one stone” approach replaces hazardous phosgene-based methods, avoids metal waste, and establishes a sustainable closed-loop recycling system with significant environmental and economic benefits.

Herein, we report a both regioselective and stereoselective method for the formation of C(sp2)-P bonds using alkenylsulfonium salts and >P(O)-H compounds. By employing a palladium catalyst or K2CO3, a variety of (E)-alkenylphosphorus compounds and terminal alkenylphosphorus compounds were successfully synthesized with high selectivity. Notably, trisubstituted (Z)-alkenylphosphorus compounds were synthesized for the first time under metal-free conditions. This protocol has a wide substrate scope and good functional group compatibility, providing a direct and highly selective approach for the preparation of various alkenylphosphorus compounds.

(Hetero)polyaryl amines are extensively prevalent in pharmaceuticals, fine chemicals, and materials but the intricate and varied nature of their structures severely restricts their synthesis. Here, we present a selective multicomponent cycloaromatization of structurally and functionally diverse amine substrates for the general and modular synthesis of (hetero)polyaryl amines through copper(I)-catalysis. This strategy directly constructs a remarkable range of amino group-functionalized (hetero)polyaryl frameworks (194 examples), including naphthalene, binaphthalene, phenanthren, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, quinoline, isoquinoline, quinazoline, and others, which are challenging or impossible to obtain using alternative methods. Copper(III)-acetylide species are involved in driving the exclusive 7-endo-dig cyclization, suppressing many side-reactions that are susceptible to occur. Due to the easy introduction of various functional units into heteropolyarylamines, multiple functionalized fluorescent dyes can be arbitrarily synthesized, which can serve as effective fluorescent probes for monitoring the pathological processes (e.g. chemotherapy-induced cell apoptosis) and studying the related disease mechanisms.

The extra-ligand-free CuTC-catalyzed C-P cross coupling reaction of propargylic acetates with H-phosphine oxides is reported to afford allenylphosphine oxides. The reaction took place efficiently with diphenylphosphine oxide and electron-deficient di(4-fluorophenyl)phosphine oxide, but less effectively with electron-rich ones such as di(4-methoxylphenyl)phosphine oxide and dialkylphosphine oxides. H-phosphine oxides themselves may serve as the ligand.

A facial protocol was developed for the synthesis of aryl-alkyl thioethers through LEDs-induced cross coupling of diaryl disulfide and alkylboronic pinacol esters assisted with N-nitrosomorpholine. This transformation proceeded efficiently under mild conditions and delivered the corresponding thioethers in good to excellent yields.

A straightforward strategy was developed for the synthesis of diaryl thioethers through the palladium-catalyzed direct desulfurization of diaryl disulfides. A wide range of aromatic disulfides (ArSSAr) were smoothly desulfurized to afford the corresponding thioethers (ArSAr) in good to high yields, overcoming the limitations of traditional phosphine-based desulfurization methods, which often exhibit sluggish reactivity with aromatic disulfides. Notably, this method was successfully extended to the synthesis of diphenyl selenide (PhSePh) and diphenyl telluride (PhTePh), which were obtained in excellent yields. Furthermore, when applied to diheteroaryl disulfides (HetSSHet, where Het = 2-pyridyl or 2-thienyl), the reaction unexpectedly afforded the corresponding diheteroaryl compounds (Het-Het) via C-C coupling, rather than the anticipated thioether products.

Phosphorus-containing unsaturated hydrocarbons, including alkenyl, allenyl, and alkynyl phosphoryl compounds, constitute a significant subclass of organophosphorus intermediates that have extensive applications in organic synthesis and related fields. Among various synthetic approaches, the transition metal-mediated reactions of the readily accessible hydrogen phosphoryl chemicals with alkynes stand out as one of the most efficient and straightforward methods for their preparation. Here, we summarize the recent advancement in transition metal-catalyzed P(O)-H alkenylation, allenylation, and alkynylation reactions to reflect a current research trend of the field.

QUINAPs represent a powerful class of ligands with broad applications in a diverse array of synthetically important asymmetric transformations. However, their broader utilization is often constrained by a limited substrate scope and high cost associated with their multistep synthesis. Consequently, a highly efficient dynamic kinetic asymmetric transformation of N-heterobiaryl derivatives has been developed through Ni-catalyzed asymmetric C-P cross-coupling. This method provides versatile access to a wide range of substituted QUINAP derivatives with good yields and high enantioselectivities, which are successfully applied in both transition-metal catalysis and organocatalysis.

We report the first successful realization of sulfenylation/phosphorylation of unactivated alkenes via thianthrenation. This strategy achieves regioselective C-S/C-P bond formation in one pot by reacting alkenylsulfonium salts with diaryl disulfides and P(O)-H reagents under basic conditions. The transition-metal- and catalyst-free protocol features mild reaction conditions and broad substrate compatibility, affording a new approach for the selective construction of sulfur- and phosphorus-embedded molecular architectures.

It was unexpectedly found that, if performed in amide type solvents such as DMF, nucleophilic substitution reaction of heteroaryl halides and thiosilanes could proceed effectively without any activator or catalyst. Mechanistic studies and literature findings implied that a DMF‐promoted direct S─Si bond activation of thiosilanes is most likely the driving force to promote the reaction. This protocol could be extended to alkyl halides and some electron‐deficient aryl halides, showing relatively broad scope of the substrates. This method may be a more convenient and practical way for preparing several types of unsymmetrical thioethers.

Reductive functionalization of aldehydes and ketones is one of the most challenging but ultimately rewarding areas in synthetic chemistry and related sciences. We report a simple and extremely versatile carbonyl reductive functionalization strategy achieving direct, highly selective, and efficient reductive amination, etherification, esterification, and phosphinylation reactions of (hetero)aryl aldehydes and ketones, which are extremely challenging or unattainable to achieve by traditional strategies, using only diphenylphosphine oxide and an inorganic base. It enables modular synthesis of functionally and structurally diverse tertiary amines, ethers, esters, phosphine oxides, etc., as well as related pesticides, drug intermediates, and pharmaceuticals. Compared to phosphorus-mediated name reactions, this strategy firstly transformed C═O bonds into C-element single bonds. Mechanistically, phosphinates are formed as intermediates, which undergo unconventional nucleophilic substitution at the C atom within their C─O─P unit. Thus, this work provides important strides in the field of reductive functionalization of aldehydes/ketones, phosphorus-mediated transformation, and various fundamental reactions.

Sodium hypophosphite (NaH2PO2) stands out as a green, safe, stable, and cost-effective phosphorus source, presenting itself as one of the promising substitutes for traditional phosphorus trichloride (PCl3). Its distinctive structure allows for the conversion of the two phosphine hydrogen bonds within its molecule into new functional groups through reactions, while the phosphate structure can be transformed into phosphonic acid or phosphonate groups. This review delineates environmentally benign NaH2PO2 appear to be the potential surrogates to PCl3 in perspective and the utilization as a phosphorus source in synthesizing phosphorus compounds over recent decades.