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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. [ABSTRACT FROM AUTHOR]

A promoter‐free chalcogenophosphorylation reaction between diverse P(O)−H reagents and chalcogenosulfonates has been developed. In the absence of metal or any other additives, these transformations proceed through a spontaneous process at room temperature, which provide a convenient and compatible approach to a broad range of selenophosphates and thiophosphates. [ABSTRACT FROM AUTHOR]

A TFAA/DMSO/NaF‐based system for the efficient fluorination of P(O)−H and P(O)−OH compounds has been developed. Without adding highly toxic and expensive fluorination reagents, this novel transformation provides direct and compatible access to a variety of fluorophosphonates and phosphonofluoridates in a one‐pot manner. [ABSTRACT FROM AUTHOR]

A palladium‐catalyzed Catellani‐type reaction of indole with diethyl (iodomethyl)phosphonate has been developed. This new protocol provides an efficient and concise route to 2‐methylene phosphonate indoles, which are key synthons for the construction of indole alkaloids. [ABSTRACT FROM AUTHOR]

The low‐cost cobalt(II) catalyst has been used for the first time to achieve P(O)‐radical‐mediated bisfunctionalization of alkenes with diarylphosphine oxide and peroxides. This simple process is performed under mild conditions to afford a wide variety of phosphonation‐peroxidation products in a one‐pot manner. Computational studies are carried out to provide a theoretical support for the P(O)‐radical‐involved bisfunctionalization of alkenes. [ABSTRACT FROM AUTHOR]

A Cerium(IV)‐promoted phosphinoylation‐nitratation of alkenes is established under mild conditions. In this process, Ceric ammonium nitrate (CAN) acts as a cheap phosphorus‐radical initiator, as well as a nitrate donor. Various β‐nitrooxyphosphonates are delivered in high yield in a one‐pot manner. [ABSTRACT FROM AUTHOR]

A new type of phosphine radical precursor for C—P bond formation has been developed and successfully used in visible‐light‐catalyzed phosphonation‐annulation of unsaturated sulfonamides and carboxylic acids. The catalytic process is simple and green accessible, and no additional oxidant or base is needed. Mechanistic studies suggest that the reaction proceeds via a single electron transfer pathway. A new type of phosphine radical precursor for C—P bond formation has been developed and successfully used in visible‐light‐catalyzed phosphonation‐annulation of unsaturated sulfonamides and carboxylic acids. The catalytic process is simple and green accessible, and no additional oxidant or base is needed. Mechanistic studies suggest that the reaction proceeds via a single electron transfer pathway. [ABSTRACT FROM AUTHOR]

Abstract: An efficient and practical method for the synthesis of α,α‐difluoro‐γ‐aminophosphonates through photocatalyzed intermolecular aminodifluoromethylphosphonation of alkenes has been developed. In this reaction, difluoromethylphosphonate is used as an important fluorinated reagent. Furthermore, the mild reaction conditions, simple operation, and broad substrate scope make this protocol very practical and attractive. The derivatization reaction in the synthesis of difluoromethylphosphonated chiral binaphthylamine ligands and α,α‐difluoro‐γ‐aminophosphoric acid highlight the applicability of this method. [ABSTRACT FROM AUTHOR]

Abstract: 3‐Phosphinoylindoles are important components of biological active natural products and materials in pharmaceuticals. Herein, a new approach for the synthesis of 3‐phosphinoylindoles has been established by a Rh(III)‐catalyzed cyclization from readily accessible (2‐azidostyryl)diphenylphosphine oxides. This intramolecular transformation occurs through a unique phosphine oxide group migration and offers a straightforward route to rebuild sp2 C−P bond and construct the indole ring in single step. [ABSTRACT FROM AUTHOR]

An efficient metal-free tandem intramolecular oxidative C−H amination and iodization of phosphinamide was performed and a series of new phosphorus heterocyclic compounds was obtained. This method provides a concise and highly valuable pathway for the synthesis of difunctional atropoisomeric P-stereogenic phosphinamides. [ABSTRACT FROM AUTHOR]

This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios. [ABSTRACT FROM AUTHOR]

Efficient asymmetric Suzuki-Miyaura coupling reactions have been employed for the first time to synthesize chiral biaryl compounds with phosphinate groups as chiral auxiliaries. A series of functionalized chiral biaryls are thereby synthesized in excellent yields and good diastereoselectivities (up to >95:5 d.r.) and axially chiral monophosphorus ligands are obtained through further functionalizations. [ABSTRACT FROM AUTHOR]

An aluminum triflate-catalyzed intramolecular reaction sequence involving protonation and Mannich-like nucleophilic addition of indoles toward the concise construction of the tetrahydropyrido[1,2- a]indol-6-one skeleton is reported. This new reaction pattern employs a carbon atom as nucleophile to form a CC bond which bears one or even two quaternary carbons and leads to the dearomatization of indoles with high atom economy. [ABSTRACT FROM AUTHOR]

A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel-catalyzed C-P bond-forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C-Cl bond. [ABSTRACT FROM AUTHOR]

Review: [30 refs. [ABSTRACT FROM AUTHOR]

Review: [21 refs. [ABSTRACT FROM AUTHOR]

Arylacrylamides (I), (IV), and (VI) are found to react with aryl bromides and benzyl chloride in the presence of a Rh-catalyst to yield oxindoles. [ABSTRACT FROM AUTHOR]

Asymmetric Suzuki – Miyaura couplings between chiral phosphine substrates and aryl bromides are used to efficiently synthesize biaryl compounds with phosphinate groups as chiral auxiliaries in excellent yields and diastereoselectivities, as described by Y. ‐ N. Ma and S. ‐ D. Yang in their Communication on page 6673 ff. [ABSTRACT FROM AUTHOR]

Review: 15 refs. [ABSTRACT FROM AUTHOR]