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.

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.

Photocatalyzed Intermolecular Aminodifluoromethylphosphonation of Alkenes: Facile Synthesis of α,α-Difluoro-γ-aminophosphonates.

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.

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.

Pd-Catalyzed Heck-Type Reaction: Synthesizing Highly Diastereoselective and Multiple Aryl-Substituted P-Ligands.

In this work, an efficient palladium-catalyzed Heck-type reaction was successfully used to synthesize a wide range of monoaryl- or diaryl-substituted P-ligands with excellent yields and diastereoselectivity (up to 98% yield, dr >20:1). The preliminary mechanistic studies demonstrated that it possibly underwent a cationic Heck reaction that was assisted by silver salt, and it revealed the significant role of P(O)Ar2 for excellent yields and diastereoselectivity.