5023-68-7

Upstream product

• 33533-58-3 phthalic acid mono-(4-methoxy-benzyl ester) 
• 106-45-6 para-thiocresol 
• 121-98-2 methyl 4-methoxybenzoate 
• 100-09-4 4-methoxybenzoic acid 
• 106-38-7 para-bromotoluene 
• 6258-60-2 p-methoxybenzylmercaptan 
• 624-31-7 4-tolyl iodide 
• 1515-81-7 1-methoxy-4-(methoxymethyl)benzene 
• 2746-25-0 p-Methoxybenzyl bromide 
• 123-11-5 4-methoxy-benzaldehyde 
• 19350-72-2 N'-(4-methoxybenzylidene)-4-methylbenzenesulfonohydrazide 
• 105-13-5 4-Methoxybenzyl alcohol 
• 824-94-2 p-methoxybenzyl chloride 

Downstream Products

• 180746-15-0 1-methoxy-4-[(p-tolylsulfinyl)methyl]benzene 
• 24845-40-7 2-(4-methoxyphenyl)acetophenone 
• 16343-36-5 2-(4-methoxy-phenyl)-2-phenylacetaldehyde 
• 1356187-42-2 2-(4-methoxyphenyl)-1-phenylpent-4-en-1-one 
• 1356187-69-3 8-{chloro(4-methoxyphenyl)[(4-tolyl)sulfinyl]methyl}-1,4-dioxaspiro[4.5]decan-8-ol 
• 1356187-88-6 9-(4-methoxyphenyl)-1,4-dioxaspiro[4.6]undecan-8-one 
• 1372784-05-8 (E)-methyl 3-{5-methoxy-2-(p-tolylthiomethyl)phenyl}acrylate 
• 1417645-76-1 C₂₂H₂₂O₂S 
• 58680-51-6 1-methoxy-4-(tosylmethyl)benzene 

Relevant academic research and scientific papers

Photoredox Nickel-Catalyzed C-S Cross-Coupling: Mechanism, Kinetics, and Generalization

Photoredox-mediated nickel-catalyzed cross-couplings have evolved as a new effective strategy to forge carbon-heteroatom bonds that are difficult to access with traditional methods. Experimental mechanistic studies are challenging because these reactions involve multiple highly reactive intermediates and perplexing reaction pathways, engendering competing, but unverified, proposals for substrate conversions. Here, we report a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling based on time-resolved transient absorption spectroscopy, Stern-Volmer quenching, and quantum yield measurements. We have (i) discovered a self-sustained productive Ni(I/III) cycle leading to a quantum yield φ > 1; (ii) found that pyridinium iodide, formed in situ, serves as the dominant quencher for the excited state photocatalyst and a critical redox mediator to facilitate the formation of the active Ni(I) catalyst; and (iii) observed critical intermediates and determined the rate constants associated with their reactivity. Not only do the findings reveal a complete reaction cycle for C-S cross-coupling, but the mechanistic insights have also allowed for the reaction efficiency to be optimized and the substrate scope to be expanded from aryl iodides to include aryl bromides, thus broadening the applicability of photoredox C-S cross-coupling chemistry.

Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis

An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.

Dithioacetalization or thioetherification of benzyl alcohols using 9-mesityl-10-methylacridinium perchlorate photocatalyst

We report herein the use of 9-mesityl-10-methylacridinium perchlorate as the visible-light photocatalyst for dithioacetalization or thioetherification of benzyl alcohols in one pot using aerial dioxygen as a terminal oxidant. EPR analysis and Stern-Volmer

Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities

Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.

Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides via Thiyl Radicals

Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C-S cross-coupling was achieved versus competitive C-O and C-N cross-couplings. This C-S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C-S cross-coupling reaction does not involve a Ni(0)-species.

Indium-Catalyzed Reductive Sulfidation of Esters by Using Thiols: An Approach to the Diverse Synthesis of Sulfides

A new reductive preparation of unsymmetrical sulfides from esters and thiols in the presence of InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 as the reductant was developed. This protocol was applied to not only benzoic acid esters that have a methoxy, methyl, chloro, bromo, iodo, or trifluoromethyl group on the aromatic ring but also aliphatic acid esters with either aromatic or aliphatic thiols. A reaction mechanism is proposed by using Hammett plot results and several control experiments. The reductive preparation of unsymmetrical sulfides from esters and thiols by using InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 was developed. Several mechanistic studies support that the present transformation proceeds through O,S-and S,S-acetals as the reaction intermediates. TMDS = 1,1,3,3-tetramethyldisiloxane, R = aliphatic group.

Silyl trifluoromethanesulfonate-activated para-methoxybenzyl methyl ether as an alkylating agent for thiols and aryl ketones

Para-Methoxybenzyl methyl ether acts as an alkylating agent for thiols in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine base in good yields (58-96%). Aryl ketones are alkylated under similar conditions, probably through an eno

Palladium-catalyzed C-H alkenylation of arenes using thioethers as directing groups

Thioethers have been proven to be reliable directing groups for palladium catalyzed alkenylation of arenes via C-H activation. Mechanistic investigation reveals that the C-H cleavage of arenes is the turnover-limiting step, and an acetate-bridged dinuclear cyclopalladation intermediate is involved. The alkenylated thioethers can be easily removed and transformed into a variety of useful groups.

Thioethers as directing group for the palladium-catalyzed direct arylation of arenes

Thioethers have proven to be efficient directing groups for the arylation of arenes under palladium catalysis. The thioether group can be readily removed or converted to other functional groups. Kinetic isotopic effect studies reveal that the C-H cleavage of arenes might be the turnover-limiting step. Copyright

Aryl(chloro)methyl 4-tolyl sulfoxides: Synthesis and application to the synthesis of α-aryl ketones

Aryl(chloro)methyl 4-tolyl sulfoxides were synthesized from arylmethyl 4-tolyl sulfoxides in moderate-to-good yields by sequential treatment with lithium diisopropylamide and tosyl chloride at low temperatures. Treatment of the lithium α-sulfinyl carbanion of the aryl(chloro)methyl 4-tolyl sulfoxides with aldehydes or ketones resulted in the formation of adducts in good-to-high yields. Treatment of these adducts with tert-butylmagnesium chloride gave the corresponding magnesium alkoxides. On treatment with isopropylmagnesium chloride, the alkoxides gave the corresponding magnesium β-oxido carbenoids, which rearranged to give α-aryl ketones in good-to-high yields. The magnesium enolate intermediates generated by rearrangement of the -oxido carbenoids could also be trapped with electrophiles to give α-aryl α-substituted ketones. These procedures offer a good method for the synthesis of a variety of α-aryl ketones from aldehydes and ketones. Georg Thieme Verlag Stuttgart. New York.