Chiral α-Aminophosphonates as Ligands in Copper-Catalyzed Asymmetric Oxidative Coupling of 2-Naphthols.

Chiral α-aminophosphonates with adjacent carbon and phosphonate stereogenic centers have been employed as ligands in the copper-catalyzed oxidative coupling of 2-naphthols, resulting in the production of chiral BINOLs in favorable yields and moderate to good enantiomeric excess. This represents the first application of chiral P-based ligands to enable such a transformation. The synthesis of these chiral α-aminophosphonate ligands offers a significant advantage over approaches that typically necessitate elaborate synthetic processes for chiral ligand production.

Tf2O-Mediated P(O)-N Bond Formation of Either P(O)-OH or P(O)-H Reagents with Multitype Amines.

We have developed a Tf2O-mediated approach for the direct amination of either P(O)-OH or P(O)-H reagents with a variety of aliphatic or aromatic amines. Without the requirement of precious metals and toxic reagents, this protocol provides an alternative route to various phosphinamides and phosphoramides. The reaction proceeds under simple and mild conditions and can be effectively scaled up with similar efficiency.

Eight-Membered Palladacycle Intermediate Enabled Synthesis of Cyclic Biarylphosphonates.

Transition-metal-catalyzed coupling reactions that involve the direct functionalization of insert C-H bond represent one of the most efficient strategies for forming carbon-carbon bonds. Herein, a palladium-catalyzed intramolecular C-H bond arylation of triaryl phosphates is reported to access seven-membered cyclic biarylphosphonate targets. The reaction is achieved via a unique eight-membered palladacyclic intermediate and shows good functional group compatibility. Meanwhile, the product can be readily converted into other valuable phosphate compounds.

Tf2O/DMSO-mediated dual activation of aryl phosphinate to access various aryl phosphonates.

A metal-free method for the dual activation of aryl phosphinate has been developed; the P-H and P-O bonds are sequentially activated by the Tf2O/DMSO system. Without the requirement of metals and unstable P-reagents, this one-pot procedure provides a convenient and practical access to a variety of aryl phosphonates. A mechanism involving twice generation of electrophilic P-species and two SN-processes is proposed on the basis of the control experiments.

Nickel-Catalyzed Sodium Hypophosphite-Participated Direct Hydrophosphonylation of Alkyne toward H-Phosphinates.

The traditional methods for the synthesis of phosphinate esters use phosphorus trichloride (PCl3) as the phosphorous source, resulting in procedures that are often highly polluting and energy intensive. The search for an alternative approach that is both mild and environmentally friendly is a challenging, yet highly rewarding task in modern chemistry. Herein, we use an inorganic phosphorous-containing species, NaH2PO2, to serve as the source of phosphorous that participates directly in the nickel-catalyzed selective alkyne hydrophosphonylation reaction. The transformation was achieved in a multicomponent fashion and at room temperature, and most importantly, the H-phosphinate product generated is an advanced intermediate which can be readily converted into diverse phosphinate derivatives, including those bearing new P-C, P-S, P-N, P-Se, and P-O bonds, thus providing a complimentary method to classic phosphinate ester synthesis techniques.

Lewis acid-catalyzed Pudovik reaction-phospha-Brook rearrangement sequence to access phosphoric esters.

Herein, we report a Lewis acid-catalyzed Pudovik reaction-phospha-Brook rearrangement sequence between diarylphosphonates or -phosphinates and α-pyridinealdehydes to access valuable phosphoric ester compounds. This transformation provides an extended substrate scope that is complementary to similar previously reported base-catalyzed transformations.

Visible-Light-Mediated Tandem Difluoromethylation/Cyclization of Alkenyl Aldehydes toward CF2H-Substituted Chroman-4-one Derivatives.

An efficient and facile visible-light-mediated tandem difluoromethylation/cyclization of alkenyl aldehydes, with easily accessible and air-stable [Ph3PCF2H]+Br- as the difluoromethylation reagent, has been established. A range of CF2H-substituted chroman-4-one skeletons and their derivatives, such as 2,3-dihydroquinolin-4(1H)-ones, chroman, 3,4-dihydronaphthalen-1(2H)-one, 2,3-dihydrobenzofuran, and 2,3-dihydro-1H-inden-1-one, are efficiently produced in moderate to good yields with excellent chemoselectivity under mild reaction conditions.

Bisphosphorylation of anhydrides - convenient access to bisphosphonates with a P-O-C-P motif.

A novel strategy of bisphosphorylation of anhydrides with P(O)-H reagents via a DMAP-catalyzed and DBU-promoted process has been developed. These one-step transformations proceed efficiently to provide convenient access to a variety of P-O-C-P motif containing organophosphorus compounds. In addition, the gram-scale synthesis and the efficient recovery of the by-product highlight the sustainability and applicability of this method.

Differences of rhizospheric and endophytic bacteria are recruited by different watermelon phenotypes relating to rind colors formation.

To elucidate the biological mechanism of yellow rind formation on watermelon, the characteristics of soil bacterial community structure in rhizosphere and endophytic bacteria in stem of yellow rind watermelon were analyzed. Based on high-throughput sequencing technology, plant stem and rhizosphere soil samples, which collected from yellow and green rind watermelons were used in this paper, respectively. The structural characteristics of the endophytic bacteria in stems and soil bacterial communities in rhizospheres of yellow and green rind watermelons were comparative studied. Firstly, significant different proportions of some dominant bacteria and abundances could be detected between yellow and rind watermelons. Meanwhile, although different abundances of endophytic bacteria could be found, but no significant differences were observed between yellow and green rind watermelons. Moreover, Gemmatimonadota, Myxococcota, WPS-2, norank_f_Gemmatimonadaceae and Bradyrhizobium were the soil dominant bacterial genera in rhizosphere of green rind watermelon. All above results suggest that differences of rhizospheric and endophytic bacteria are exactly recruited as "workers" by different watermelon phenotypes relating to rind color formations.

Transition-metal-free three-component coupling approach to QUINAP derivatives.

The aluminum(III) triflate catalyzed three-component coupling reaction of alkynes, amines and phosphorylated aryl aldehydes to access phosphoryl quinoline derivatives has been developed. The reaction proceeds in a simple system without the use of transition metals, ligands or additives, thus making it attractive for the fast preparation of a variety of new potential N-P bidentate ligands.

Primary Amination of Ar2P(O)-H with (NH4)2CO3 as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P-N or P-O Bonds.

A facile and efficient method for the synthesis of primary phosphinamides from Ar2P(O)-H reagents with stable and readily available ammonium carbonate as an ammonia source is disclosed herein for the first time. This ethyl bromoacetate-mediated primary amination proceeds smoothly under mild and simple conditions, without any metal catalyst or oxidant. Moreover, this method is also appropriate for the reaction of Ar2P(O)-H with a variety of amines, alcohols, and phenols to construct P-N or P-O bonds, with features of handy operation, good functional group tolerance, and broad substrate scope.

Heck Reaction Boosted Heterocycle Ring-Closing and Ring-Opening Rearrangement: A Strategy for the Synthesis of Indolyl-Type Ligands.

A novel method for P-involved heterocycle ring-closing-ring-opening rearrangement (HRR) via the Heck reaction is disclosed. The approach enables direct installation of a phosphorus-containing aryl group onto the C2 position of indole. This new rearrangement directly transforms easily prepared indole derivatives into indolyl-derived phosphonates and phosphinic acids with high yields, and many of the products are difficult to obtain by using established methods. This new HRR reaction provides an extremely simple and step-economic method to induce C-C bond formation and P-N bond cleavage for the synthesis of a variety of indolyl-type ligands.

Recent advances in the synthesis and applications of phosphoramides.

Phosphoramide, as an important framework of many biologically active molecules, has attracted widespread attention in recent decades. It is not only widely used in pharmaceuticals because of its excellent biological activities, but it also shows good performance in organic dyes, flame retardants and extractors. Thus, it is of great significance to develop effective and convenient methods for the synthesis of phosphoramides. In this review, the recent advancements made in the synthesis routes and applications of phosphoramides are discussed. The synthetic strategies of phosphoramides can be separated into five categories: phosphorus halides as the substrate, phosphates as the substrate, phosphorus hydrogen as the substrate, azides as the substrate and other methods. The latest examples of these methods are provided and some representative mechanisms are also described.

Visible-light-facilitated P-center radical addition to C[double bond, length as m-dash]X (X = C, N) bonds results in cyclizations.

Visible-light-facilitated phosphorus radical reactions have been developed as a powerful and sustainable tool for the synthesis of various organophosphorus compounds. In general, these reactions require stoichiometric amounts of oxidants, and reductants, bases, and radical initiators, leading to uneconomical and complicated processes. Progress has been made over the past few years toward using reactions that proceed under eco-benign and mild reaction conditions. Furthermore, these reactions have broad functional group tolerance, with some facile and economical pathways. Herein, we summarize the discoveries and achievements pertaining to C-P bond formation through a visible light photocatalysis procedure with high atom economy, made by our group and other research groups. It was established that greener and more environmentally friendly approaches do not require an additional oxidant or base. Moreover, we have designed and synthesized a new type of P-radical precursor, which can take part in reactions without the requirement for any additional bases, oxidants, and additives. This breakthrough, pertaining to novel visible-light-induced transformations, will be discussed and a plausible mechanism is proposed, based on corresponding experiments and the literature.

Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates.

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.

Temporary (P[double bond, length as m-dash]O) directing group enabled carbazole ortho arylation via palladium catalysis.

A palladium-catalyzed, temporary P(O) directing group assisted C-H bond arylation of carbazoles was achieved. The release of the directing group occurs spontaneously in the reaction and the mechanistic studies indicate that acid is essential for N-P bond cleavage.

Ir(III)-Catalyzed C-H Functionalization of Triphenylphosphine Oxide toward 3-Aryl Oxindoles.

With triphenylphosphine oxide serving as both the directing group and the reagent, we have developed a Cp*Ir(III)-catalyzed direct C-H functionalization of triphenylphosphine oxide with 3-diazooxindoles to afford a range of 3-(2-(diphenylphosphoryl)phenyl)indolin-2-one derivatives in moderate to excellent yields. The title products are potentially important building blocks for organic synthesis through various chemical transformations. This protocol is simple and efficient and offers high atom economy with only N2 as the byproduct.

Bismuth(III)-Catalyzed Sequential Enamine-Imine Tautomerism/2-Aza-Cope Rearrangement of Stable ß-Enaminophosphonates: One-Pot Synthesis of ß-Aminophosphonates.

A novel catalytic tautomeric transformation of a ß-enaminophosphoryl and 2-aza-Cope rearrangement sequence has been successfully applied to the one-pot synthesis of ß-aminophosphonates with high efficiency and good tolerance. In this tandem reaction, Bi(OTf)3 exhibits unique activities and promotes both of enamine-imine tautomerism and 2-aza-Cope rearrangement.

Visible photocatalysis of novel oxime phosphonates: synthesis of ß-aminophosphonates.

A novel type of oxime phosphonate was synthesized and used in the intermolecular cascade radical addition reaction of alkenes to access ß-aminophosphonates via visible-light-driven N-centered iminyl radical-mediated and redox-neutral selective C-P single-bond cleavage in an active phosphorus radical route. The procedure is characterized by its ability to achieve the construction of Csp3-P and Csp3-N bonds without the requirement for oxidants and bases.