Yuzhen Gao

Copper-Catalyzed P-Arylation via Direct Coupling of Diaryliodonium Salts with Phosphorus Nucleophiles at Room Temperature

A new method for copper-catalyzed P-C bond formation through reaction of phosphorus nucleophiles with diaryliodonium salts at room temperature is described. Most target products are obtained with this method in high yields within a short reaction time of 10 min. It can be easily adapted to large-scale preparations. When unsymmetrical iodonium salts are employed, nucleophilic substitution occurs preferentially on the sterically hindered aromatic ring or the more electron-deficient ring.

A Cascade Phosphinoylation/Cyclization/Desulfonylation Process for the Synthesis of 3-Phosphinoylindoles

3-Phosphinoylindole derivatives play important roles as pharmaceutical drugs and ligands. A new method for the synthesis of 3-phosphinoylindole derivatives has been achieved through silver-mediated cycloaddition between N-Ts-2-alkynylaniline derivatives and H-phosphine oxides. This transformation offers a straightforward route to the formation of the C-P bond, indole ring, and desulfonylation in one step.

Direct Transformation of Amides into α-Amino Phosphonates via a Reductive Phosphination Process

The first general method for the reductive phosphination of amides in one pot has been developed. The reactions described provide a novel access to α-amino phosphonates in good to excellent yields, cover a broad scope of substrates such as secondary and tertiary amides, and do not require a low temperature.

tert-Butyl Hydroperoxide Mediated Cascade Synthesis of 3-Arylsulfonylquinolines

3-Arylsulfonylquinoline derivatives play important roles as pharmaceutical drugs. A new method for the synthesis of 3-arylsulfonylquinoline derivatives has been achieved through tert-butyl hydroperoxide mediated cycloaddition between N-propargyl aromatic amine derivatives and arylsulfonylhydrazides without the addition of any metals. This transformation offers a straightforward route to the formation of a C-S bond and quinoline ring in one step via a sulfonylation-cyclization-aromatization process.

Cascade arylalkylation of activated alkenes: synthesis of chloro- and cyano-containing oxindoles.

The general method for the oxidative cyclization of arylacrylamides with dichloromethane or acetonitrile has been developed. The reactions described provide novel access to chloro- and cyano-containing oxindoles in good to moderate yields that allow the direct formation of a C-C bond and the construction of an oxindole ring in one reaction. The use of a cheap and easily prepared Mn(OAc)3 represents an added advantage of this method.

Phosphorothiolation of Aryl Boronic Acids Using P(O)H Compounds and Elemental Sulfur

The first multicomponent reaction (MCR) involving aryl boronic acids, elemental sulfur, and P(O)H compounds is presented. It proceeds with excellent yields and provides an attractive approach for the construction of valuable S-aryl phosphorothioates and S-aryl phosphorodithioates using a one-step strategy. Moreover, this method can be easily adapted to large-scale preparation.

Copper-Catalyzed Phosphonation–Annulation Approaches to the Synthesis of β-Phosphonotetrahydrofurans Involving C–P and C–O Bonds Formation

Substituted tetrahydrofuran derivatives play important roles as biological activities. A versatile method for the synthesis of β-phosphonotetrahydrofurans has been developed based on Cu-catalyzed difunctionalization of alkenes. This transformation would provide a new pathway for the formation of Csp(3)-P and Csp(3)-O bonds in one step. Furthermore, this copper catalyst system can be used in the synthesis of β-phosphonotetrahydropyrans and phosphono-γ-butyrolactones. These reactions were also performed well by using 3 equiv of Mn(OAc)3·2H2O as the oxidant without copper catalyst.

Mn(OAc)3-mediated synthesis of β-hydroxyphosphonates from P(O)–H compounds and alkenes

A new and general method for the synthesis of β-hydroxy phosphonates has been achieved through Mn(OAc)3-mediated radical oxidative phosphonation of alkenes with H-phosphonates and H-phosphine oxide. The starting materials of P(O)–H compounds and alkenes are stable and cheap. Mn(OAc)3 can be readily prepared from Mn(OAc)2 in the laboratory. This method can be easily adapted to large-scale preparations.

Copper-catalyzed cycloaddition between hydrogen phosphonates and activated alkenes: synthesis of phosphonoisoquinolinediones

A new, general method for the synthesis of phosphonoisoquinolinediones has been achieved via copper-catalyzed phosphonation–cyclization of various methacryloylbenzamides with P(O)H compounds. This transformation allows the direct formation of a P–C bond and the construction of an isoquinolinedione ring in one reaction.

Synthesis of 3-phosphinoylquinolines via a phosphinoylation–cyclization–aromatization process mediated by tert-butyl hydroperoxide

The first metal-free phosphinoylation–cyclization–aromatization method has been developed. The present methodology produces a series of substituted 3-phosphinoylquinolines in moderate to good yields from N-propargylanilines and H-phosphine oxides mediated by tert-butyl hydroperoxide.