Xiaojun Zeng

Synthesis of α‐Fluoroketones by Insertion of HF into a Gold Carbene

Reported is an efficient synthesis of α-fluoroketones by insertion of hydrogen fluoride (HF) into the gold carbene intermediate, generated from a cationic gold catalyzed addition of N-oxides to alkynes. This method results in excellent chemical yields for a wide range of alkyne substrates and demonstrates good functional-group tolerance.

(Radio)fluoroclick Reaction Enabled by a Hydrogen‐Bonding Cluster

We have developed a widely applicable nucleophilic (radio)fluoroclick reaction of ynamides with readily available and easy-to-handle KF(18 F). The reactions exhibited high functional-group tolerance and needed only an ambient atmosphere. This 18 F addition to C-C unsaturated bonds proceeded with extraordinarily high radiochemical yields.

Divergent Regio- and Stereoselective Gold-catalyzed Synthesis of α-Fluorosulfones and β-Fluorovinylsulfones from Alkynylsulfones

We developed a widely applicable, highly efficient synthesis of α-fluorosulfone and β-fluorovinylsulfone catalyzed by gold. Starting with alkynyl sulfone 1, an [Au]/HF/N-oxide system gives α-fluorosulfone 3 via a gold carbene intermediate, and, if no N-oxide is used, direct addition of HF to 1 gives vinyl sulfone 4 via a vinylfluoro gold intermediate. Both methods have good functional group tolerance and the reactions can be conducted in ambient atmosphere.

Metal-free, Regio-, and Stereo-Controlled Hydrochlorination and Hydrobromination of Ynones and Ynamides

We developed an atom-economical and metal-free method for the regio- and stereo-selective hydrohalogenation of ynones and ynamides using easy to handle DMPU/HX (X = Br or Cl) reagents. The reaction operates under mild conditions and a range of functional groups is well tolerated. We propose that the hydrohalogenation of ynones gives the anti-addition products via a concerted multimolecular AdE3 mechanism and that the hydrohalogenation of ynamides produces the syn-addition products via a cationic keteniminium intermediate.

Gold-catalyzed Fluorination of Alkynyl Esters and Ketones: Efficient Access to Fluorinated 1,3-Dicarbonyl Compounds

We developed an efficient synthesis of 2-fluoro-1,3-dicarbonyl compounds using readily available alkynyl ketones or esters as starting material. The key step is the insertion of hydrogen fluoride (HF) to the gold carbene intermediate generated from cationic gold catalyzed addition of N-oxides to alkynyl ketones or esters. This method gives excellent chemical yields and regioselectivity with good functional group tolerance.

Stable yet reactive cationic gold catalysts with carbon based counterions

L–Au–[TsC(CN)2] are new cationic gold catalysts with a carbon based counterion, which are widely applicable for gold catalyzed reactions. For reactions which need highly reactive gold catalysts, a Lewis acid co-catalyst can be added to increase the reactivity of L–Au–[TsC(CN)2]. L–Au–[TsC(CN)2] also have advantages of easy reaction steps and high functional group tolerance.

Hydrogen-Bonding-Assisted Brønsted Acid and Gold Catalysis: Access to Both (E)- and (Z)-1,2-Haloalkenes via Hydrochlorination of Haloalkynes

We have developed an efficient synthesis of both (Z)- and (E)-chlorohaloalkenes via hydrochlorination of haloalkynes, based on two distinct hydrogen-bond-network-assisted catalytic systems: Brønsted acid catalysis and gold catalysis. Both systems offer high stereoselectivity, good chemical yields, and diverse functional group tolerance.

Widely Applicable Hydrofluorination of Alkenes via Bifunctional Activation of Hydrogen Fluoride

Expanding the use of fluorine in pharmaceuticals, agrochemicals and materials requires a widely applicable and more efficient protocol for the preparation of fluorinated compounds. We have developed a new generation nucleophilic fluorination reagent, KHSO4-13HF, HF 68 wt/wt %, that is not only easily handled and inexpensive but also capable of hydrofluorinating diverse, highly functionalized alkenes, including natural products. The high efficiency observed in this reaction hinges on the activation of HF using a highly “acidic” hydrogen bond acceptor.