64806-63-9

Upstream product

• 139-02-6 sodium phenoxide 
• 104-52-9 phenylpropyl chloride 
• 589-10-6 phenoxyethyl bromide 
• 122-97-4 3-Phenyl-1-propanol 
• 104-54-1 3-Phenylpropenol 
• 4392-24-9 Cinnamyl bromide 
• 939990-21-3 1-iodo-2-(3-phenylpropoxy)benzene 
• 1011717-62-6 1-bromo-2-(3-phenylpropoxy)benzene 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 4119-41-9 1-iodo-3-phenylpropan 
• 1821-12-1 4-Phenylbutyric acid 
• 1841512-58-0 1,3-dioxoisoindolin-2-yl 4-phenylbutanoate 
• 81416-37-7 4-methylphenyldiphenylsulfonium trifluoromethanesulfonate 
• 66003-78-9 triphenylsulfonium trifluoromethanesulfonate 

Downstream Products

• 15185-05-4 4-phenylcoumarin 
• 14794-60-6 N-Hydroxy-2-[4-(3-phenyl-propoxy)-phenyl]-acetamide 
• 15560-84-6 [4-(3-Phenyl-propoxy)-phenyl]-acetic acid ethyl ester 
• 637-59-2 1-Bromo-3-phenylpropane 

Relevant academic research and scientific papers

Structure and reactivity in neutral organic electron donors derived from 4-dimethylaminopyridine

The effects on the redox properties of modifying the molecular skeleton of neutral bis-2-(4-dimethylamino)pyridinylidene electron donors, derived from 4-dimethylaminopyridine (4-DMAP), have been explored, by varying two parameters: (i) the length of a polymethylene chain linking the two pyridine-derived rings and (ii) the nature of the nitrogen substituents on the 4 and 4″ positions of the precursor pyridines. Restricting the bridge length to two methylene units significantly altered the redox profile, while changes in the nitrogen-substituents at the 4 and 4' positions led to only slight changes in the redox potentials.

Photochemical Decarboxylative C(sp3)-X Coupling Facilitated by Weak Interaction of N-Heterocyclic Carbene

While N-hydroxyphthalimide (NHPI) ester has emerged as a powerful reagent as an alkyl radical source for a variety of C-C bond formations, the corresponding C(sp3)-N bond formation is still in its infancy. We demonstrate herein transition-metal-free decarboxylative C(sp3)-X bond formation enabled by the photochemical activity of the NHPI ester-NaI-NHC complex, giving primary C(sp3)-(N)phth, secondary C(sp3)-I, or tertiary C(sp3)-(meta C)phth coupling products. The primary C(sp3)-(N)phth coupling offers convenient access to primary amines.

Base-Mediated O-Arylation of Alcohols and Phenols by Triarylsulfonium Triflates

A mild and efficient protocol for O-arylation of alcohols and phenols (ROH) by triarylsulfonium triflates was developed under transition-metal-free conditions. Various alcohols, including primary, secondary and tertiary, and phenols bearing either electron-donating or electron-withdrawing groups on the aryl rings were smoothly converted to form the corresponding aromatic ethers in moderate to excellent yields. The reactions were conducted at 50 or 80 °C for 24 h in the presence of a certain base and showed good functional group tolerance. The base-mediated arylation with asymmetric triarylsulfonium salts could selectively transfer the aryl groups of sulfoniums to ROH, depending on their inherent electronic nature. The mechanistic studies revealed that the reaction might proceed through the nucleophilic attack of the in situ formed alkoxy or phenoxy anions at the aromatic carbon atoms of the C?S bonds of triarylsulfonium cations to furnish the target products.

Base-Free Generation of Organic Electron Donors from Air-Stable Precursors

Organic electron donors (OEDs) are powerful reducing agents recognized for their potential in the reduction of challenging substrates and in original applications. Nonetheless, their low stability in atmospheric oxygen or over time complicates their manipulation and storage. To overcome these constraints and enhance OED practicality, new air- and moisture-stable aminopyridinium carboxylate and carbonate precursors were synthesized and thermally activated to generate the potent electron donor in situ. Carboxylate adducts proved to be excellent latent OED systems, enabling the facile and efficient reduction of challenging substrates. Their reduction properties were correlated to their structural characteristics by thermogravimetric and spectroscopic analysis.

Systematic Evaluation of 2-Arylazocarboxylates and 2-Arylazocarboxamides as Mitsunobu Reagents

2-Arylazocarboxylate and 2-arylazocarboxamide derivatives can serve as replacements of typical Mitsunobu reagents such as diethyl azodicarboxylate. A systematic investigation of the reactivity and physical properties of those azo compounds has revealed that they have an excellent ability as Mitsunobu reagents. These reagents show similar or superior reactivity as compared to the known azo reagents and are applicable to the broad scope of substrates. pKa and steric effects of substrates have been investigated, and the limitation of the Mitsunobu reaction can be overcome by choosing suitable reagents from the library of 2-arylazocarboxylate and 2-aryl azocarboxamide derivatives. Convenient recovery of azo reagents is available by one-pot iron-catalyzed aerobic oxidation, for example. SC-DSC analysis of representative 2-arylazocarboxylate and 2-arylazocarboxamide derivatives has shown high thermal stability, indicating that these azo reagents possess lower chemical hazard compared with typical azo reagents.

Metal-Free I2-Catalyzed Highly Selective Dehydrogenative Coupling of Alcohols and Cyclohexenones

The I2 catalyzed highly selective oxidative condensation of cyclohexenones and alcohols for the synthesis of aryl alkyl ethers has been described. DMSO is employed as the mild terminal oxidant. This novel methodology offers a metal-free reaction condition, operational simplicity and broad substrate scope to afford valuable products from inexpensive reagents. Various meta-substituted aromatic ethers which are hardly synthesized from the reported methods requiring meta-substituted phenols, are efficiently prepared by the present protocol.

Manganese-Mediated C?H Alkylation of Unbiased Arenes Using Alkylboronic Acids

The alkylation of arenes is an essential synthetic step of interest not only from the academic point of view but also in the bulk chemical industry. Despite its limitations, the Friedel–Crafts reaction is still the method of choice for most of the arene alkylation processes. Thus, the development of new strategies to synthesize alkyl arenes is a highly desirable goal, and herein, we present an alternative method to those conventional reactions. Particularly, a simple protocol for the direct C?H alkylation of unbiased arenes with alkylboronic acids in the presence of Mn(OAc)3?2H2O is reported. Primary or secondary unactivated alkylboronic acids served as alkylating agents for the direct functionalization of representative polyaromatic hydrocarbons (PAHs) or benzene. The results are consistent with a free-radical mechanism.

Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene

A new ground-state organic electron donor has been prepared that features four strongly π-donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of ?1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S N bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.

From insertion to multicomponent coupling: Temperature dependent reactions of arynes with aliphatic alcohols

The temperature dependent selectivity switch in the reaction of arynes with aliphatic alcohols in THF has been reported. At -20°C, arynes smoothly insert into the O-H bond of alcohols to form alkyl aryl ethers. Interestingly, at 60°C, a highly selective multicomponent coupling occurs with the solvent THF acting as the nucleophilic trigger affording (4-(alkoxy)butoxy)arenes.

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.