87273-96-9

Upstream product

• 1443-80-7 4-cyanophenyl methyl ketone 
• 100-58-3 phenylmagnesium bromide 
• 16002-63-4 phenylmagnesium iodide 
• 3058-39-7 4-iodobenzonitrile 
• 98-86-2 acetophenone 
• 623-00-7 4-bromobenzenecarbonitrile 
• 623-26-7 terephthalonitrile 
• 98-85-1 1-Phenylethanol 

Downstream Products

• 169266-95-9 4-(2-methoxy-1-phenylethyl)benzonitrile 
• 23450-31-9 4-benzylbenzonitrile 
• 81329-28-4 1-(4-cyanophenyl)-1-phenylethylene 

Relevant academic research and scientific papers

Synthesis of Polyfunctionalized Triaryllanthanum Reagents by Using Ph3La and Related Species as Exchange Reagents

Ph3La?5 LiCl and the related (m-xylyl)3La?5 LiCl were used as Hal/La exchange reagents (Hal=Br, I) for the preparation of various triaryl- and triheteroaryl-lanthanum derivatives. These new exchange reagents are compatible with isoquinolines and some functional groups such as a nitrile or an ester. The reactivity of the resulting lanthanum compounds towards electrophiles, such as ketones, aldehydes, N,N-dimethylamides, and primary alkyl halides was investigated. Additionally, a Pd-catalyzed cross-coupling procedure with aryl bromides was developed.

Electrochemical Arylation of Aldehydes, Ketones, and Alcohols: from Cathodic Reduction to Convergent Paired Electrolysis

Arylation of carbonyls, one of the most common approaches toward alcohols, has received tremendous attention, as alcohols are important feedstocks and building blocks in organic synthesis. Despite great progress, there is still a great gap to develop an ideal arylation method featuring mild conditions, good functional group tolerance, and readily available starting materials. We now show that electrochemical arylation can fill the gap. By taking advantage of synthetic electrochemistry, commercially available aldehydes (ketones) and benzylic alcohols can be readily arylated to provide a general and scalable access to structurally diverse alcohols (97 examples, >10 gram-scale). More importantly, convergent paired electrolysis, the ideal but challenging electrochemical technology, was employed to transform low-value alcohols into more useful alcohols. Detailed mechanism study suggests that two plausible pathways are involved in the redox neutral α-arylation of benzylic alcohols.

Sulfonamides as new hydrogen atom transfer (HAT) catalysts for photoredox allylic and benzylic C-H arylations

A catalytic amount of a sterically and electronically tuned diarylsulfonamide promoted allylic and benzylic C-H arylations in cooperation with a visible light photoredox catalyst. This is the first example of the catalytic use of a sulfonamidyl radical to promote the hydrogen atom transfer process.

Preparation of Functionalized Diaryl- and Diheteroaryllanthanum Reagents by Fast Halogen–Lanthanum Exchange

Aryl and heteroaryl halides (X=Br, I) undergo a fast and convenient halogen–lanthanum exchange with nBu2LaMe, which leads to functionalized diaryl- and diheteroaryllanthanum derivatives. Subsequent trapping reactions with selected electrophiles, such as ketones, aldehydes, or amides, proceeded smoothly at ?50 °C in THF, affording polyfunctionalized alcohols and carbonyl derivatives. Kinetic competition experiments revealed a similar reactivity trend as for Br/Mg exchange, but 106-times higher rates, making it comparable to Br/Li exchange.

A general strategy for organocatalytic activation of c-h bonds via photoredox catalysis: Direct arylation of benzylic ethers

Direct C-H functionalization and arylation of benzyl ethers has been accomplished via photoredox organocatalysis. The productive merger of a thiol catalyst and a commercially available iridium photoredox catalyst in the presence of household light directly affords benzylic arylation products in good to excellent yield. The utility of this methodology is further demonstrated in direct arylation of 2,5-dihydrofuran to form a single regioisomer.

Reaction of Grignard reagents with carbonyl compounds under continuous flow conditions

This contribution details how a continuous flow reactor was used to react carbonyl compounds with Grignard reagents at room temperature in an efficient and safe manner. Flow rate, residence time and temperature were optimized for the preparation of a small collection of secondary and tertiary alcohols. Excellent yields and general applicability were observed using the set-up protocol. The procedure was also applied for the preparation of Tramadol, an analgesic drug belonging to the opioid group. The developed conditions allowed the selective addition of Grignard reagents to aldehydes and ketones in the presence of a nitrile function.

The effect of meta- or para-cyano substitution on the reactivity of the radical cations of arylalkenes and alkanes. Radical ions in photochemistry, Part 34

The effect of electron-withdrawing substituents, meta- or para-cyano, on the reactivity of the radical cation of arylalkenes and alkanes has been determined.The radical cations were generated by single electron transfer (set) to an electron-accepting photosensitizer.Three reactions were studied: (i) the addition of nucleophile to the radical cation of arylalkanes, (ii) cleavage of the benzylic carbon-carbon bond of the radical cation of arylalkanes; and (iii) the deprotonation of the benzylic carbon-hydrogen bond of the radical cation of arylalkanes.The radical cations of 4-(1-phenylethenyl)benzonitrile (1b), 3-(1-phenylethenyl)benzonitrile (1c), 4-(2-methoxy-1-phenylethyl)benzonitrile (2b), 3-(2-methoxy-1-phenylethyl)benzonitrile (2c), cis- and trans-5-cyano-2-methoxy-1-phenylindane (6b-cis and -trans), and 6-cyano-3-phenylindene (7b) were generated, by single electron transfer to the lowest excited singlet state of 1,4-dicyanobenzene (3), in acetonitrile-methanol.The radical cations of 1b, 1c, and 7b react with methanol to yield the anti-Markovnikov adducts (2b, 2c, and 6b-cis and 6b-trans).The radical cations of 2b, 2c, and 6b-trans cleave at the benzylic carbon-carbon bond to give products derived from the radical and carbocation fragments.The radical cation of 6b-cis deprotonates from the benzylic position with subsequent formation of the diastereomer, 6b-trans.This behaviour can be explained/predicted on the basis of the proposed mechanisms for these reactions.Molecular orbital calculations (AM1) support the conclusions.Key words: photosensitized, electron transfer, radical ions, radicals, molecular orbital calculations (AM1).

ARYL REARRANGEMENT ON THE PHOTOLYSIS OF 2-ARYL-2-ETHOXY-2-PHENYLETHYL CABALOXIME.

The photolysis of 2-aryl-2-ethoxy-2-phenylethyl cobaloxime followed by hydrolysis gave two kinds of substituted 1,2-diphenylethanones arising via phenyl or substituted-phenyl migration. The substituent effect on the aryl rearrangement is similar to that on the reported neophyl rearrangement, and the rearrangement takes place by a radical mechanism without the deep involvement of cobaloxine(II).