16473-18-0

Upstream product

• 6971-51-3 3-methoxybenzyl alcohol 
• 108087-83-8 [(3-methoxyphenyl)methylidene]hydrazine 
• 591-31-1 3-methoxy-benzaldehyde 
• 2398-37-0 3-methoxyphenyl bromide 
• 373-52-4 bromofluoromethane 
• 10365-98-7 3-methoxyphenylboronic acid 
• 373-53-5 fluoroiodomethane 
• 325142-84-5 3-methoxyphenylboronic acid pinacol ester 
• 874-98-6 1-bromomethyl-3-methoxybenzene 

Downstream Products

• 107417-55-0 3-(1-piperidinomethyl)-anisole 
• 1798-09-0 m-methoxyphenylacetic acid 
• 122439-14-9 4-[(3-methoxyphenyl)methyl]morpholine 

Relevant academic research and scientific papers

Selective Fluorination of Substituted Methanols with Methanesulfonyl Fluoride and Cesium Fluoride as Modified with Crown Ethers

A new combination of methanesulfonyl fluoride and cesium fluoride as modified with 18-crown-6 was demonstrated to be the best for selective fluorination of various benzyl alcohols via nucleophilic substitution.As extended applications of this procedure, ethyl 1-fluoromethylpyrazole-4-carboxylate (6) and N-fluoromethylphthalimide (12) have been synthesized in high yields from the corresponding alcohol (4) and chloride (11) respectively.

Deoxyfluorination of alcohols with aryl fluorosulfonates

Aryl fluorosulfonates are developed as a deoxyfluorinating reagent in the transformation of primary and secondary alcohols into the corresponding alkyl fluorides. These reagents feature easy availability, low-cost, high stability and high efficiency. Diverse functionalities including aldehyde, ketone, ester, halogen, nitro, alkene, and alkyne are well tolerated under mild reaction conditions.

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)?F bonds with CO2

It is highly attractive and challenging to utilize carbon dioxide (CO2), because of its inertness, as a nontoxic and sustainable C1 source in the synthesis of valuable compounds. Here, we report a novel selective carboxylation of C(sp3)?F bonds with CO2 via visible-light photoredox catalysis. A variety of mono-, di-, and trifluoroalkylarenes as well as α,α-difluorocarboxylic esters and amides undergo such reactions to give important aryl acetic acids and α-fluorocarboxylic acids, including several drugs and analogs, under mild conditions. Notably, mechanistic studies and DFT calculations demonstrate the dual role of CO2 as an electron carrier and electrophile during this transformation. The fluorinated substrates would undergo single-electron reduction by electron-rich CO2 radical anions, which are generated in situ from CO2 via sequential hydride-transfer reduction and hydrogen-atom-transfer processes. We anticipate our finding to be a starting point for more challenging CO2 utilization with inert substrates, including lignin and other biomass.

Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides

We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

Nickel-catalyzed monofluoromethylation of (hetero)aryl bromides via reductive cross-coupling

A mild and efficient nickel-catalyzed direct monofluoromethylation of (hetero)aryl bromides by reductive cross-coupling has been developed. This method exhibits good efficiency, wide functional-group compatibility, and suitability for aryl and heteroaryl bromides with abundant industrial raw material BrCH2F. This strategy provides an efficient way to synthesize monofluoromethylated molecules for drug discovery.

9-Borabicyclo[3.3.l]nonane-induced Friedel-Crafts benzylation of arenes with benzyl fluorides

Friedel-Crafts benzylation of arenes with benzyl fluorides using 9-borabicyclo[3.3.l]nonane (9-BBN) as a mediator has been developed. This provides a simple and cheap route to the activation of C-F bonds to synthesize 1,1-diarylmethanes in good to excellent yields (up to 98%) under mild conditions. Functional group tolerance and the mechanism are considered.

Denitrogenative hydrofluorination of aromatic aldehyde hydrazones using (difluoroiodo)toluene

An operationally simple conversion of aromatic aldehyde hydrazones to monofluoromethylated arenes is reported. The hypervalent iodine reagent TolIF2 serves as an oxidant, converting the hydrazone to the corresponding diazo compounds. The by-product of the oxidation process, HF, is consumed in situ by a denitrogenative hydrofluorination reaction of the diazo group.

Palladium-Catalyzed Monofluoromethylation of Arylboronic Esters with Fluoromethyl Iodide

The first palladium-catalyzed direct monofluoromethylation of arylboronic esters to produce monofluoromethyl arenes is reported. The reaction is typically carried out at room temperature within 4 h and has a good functional group tolerance. The monofluoromethylating agent, CH2FI, was readily prepared via a halogen-exchange process.

Efficient SN2 fluorination of primary and secondary alkyl bromides by copper(I) fluoride complexes

Copper(I) fluoride complexes ligated by phenanthroline derivatives have been synthesized and structurally characterized by X-ray crystallography. These complexes adopt as either ionic or neutral forms in the solid state, depending on the steric bulkiness of the substituent groups on the phenanthroline ligands. These complexes react with primary and secondary alkyl bromides to produce the corresponding alkyl fluorides in modest to good yields. This new method is compatible with a variety of important functional groups such as ether, thioether, amide, nitrile, methoxyl, hydroxyl, ketone, ester, and heterocycle moieties.

Triol-promoted activation of C-F bonds: Amination of benzylic fluorides under highly concentrated conditions mediated by 1,1,1-tris(hydroxymethyl) propane

Activation of the C-F bond of benzylic fluorides was achieved using 1,1,1-tris(hydroxymethyl)propane (2) as a hydrogen bonddonating agent. Investigations demonstrated that hydrogen bond-donating solvents are promoting the activation and hydrogen bondaccepting ones are hindering it. However, the reaction is best run under highly concentrated conditions, where solvents cannot interfere with the interaction between the organofluorine compound and the triol. Various benzylic fluorides react with secondary amines or anilines to form benzylic amines in good yields.