130778-69-7

Upstream product

• 591-51-5 phenyllithium 
• 66-99-9 β-naphthaldehyde 
• 591-50-4 iodobenzene 
• 77196-31-7 2-(dimethoxymethyl)naphthalene 
• 612-55-5 2-iodonaphthalene 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 100-58-3 phenylmagnesium bromide 
• 35060-38-9 (2-naphthyl)phenylmethanol 
• 74-88-4 methyl iodide 
• 67-56-1 methanol 

Downstream Products

• 42372-45-2 1-(2-naphthyl)-1-phenyl ethane 
• 613-59-2 2-benzylnaphthalene 

Relevant academic research and scientific papers

A Unified Explanation for Chemoselectivity and Stereospecificity of Ni-Catalyzed Kumada and Cross-Electrophile Coupling Reactions of Benzylic Ethers: A Combined Computational and Experimental Study

Ni-catalyzed C(sp3)-O bond activation provides a useful approach to synthesize enantioenriched products from readily available enantioenriched benzylic alcohol derivatives. The control of stereospecificity is key to the success of these transformations. To elucidate the reversed stereospecificity and chemoselectivity of Ni-catalyzed Kumada and cross-electrophile coupling reactions with benzylic ethers, a combined computational and experimental study is performed to reach a unified mechanistic understanding. Kumada coupling proceeds via a classic cross-coupling mechanism. Initial rate-determining oxidative addition occurs with stereoinversion of the benzylic stereogenic center. Subsequent transmetalation with the Grignard reagent and syn-reductive elimination produce the Kumada coupling product with overall stereoinversion at the benzylic position. The cross-electrophile coupling reaction initiates with the same benzylic C-O bond cleavage and transmetalation to form a common benzylnickel intermediate. However, the presence of the tethered alkyl chloride allows a facile intramolecular SN2 attack by the benzylnickel moiety. This step circumvents the competing Kumada coupling, leading to the excellent chemoselectivity of cross-electrophile coupling. These mechanisms account for the observed stereospecificity of the Kumada and cross-electrophile couplings, providing a rationale for double inversion of the benzylic stereogenic center in cross-electrophile coupling. The improved mechanistic understanding will enable design of stereoselective transformations involving Ni-catalyzed C(sp3)-O bond activation.

Nickel-Mediated Enantiospecific Silylation via Benzylic C-OMe Bond Cleavage

Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C-C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.

Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons

A series of aromatic hydrocarbons were investigated so as to compare the reactivity of corannulene with planar aromatic hydrocarbons. Corannulene was found to be more reactive than benzene, naphthalene and triphenylene to Friedel-Crafts acylation whilst electrophilic aromatic bromination was also used to confirm that triphenylene was less reactive than corannulene and that pyrene, perylene and acenaphthene were more so. The stabilisation of a neighbouring carbocation by the various aromatic systems was investigated through consideration of the rates of methanolysis of a series of benzylic alcohols. The reactivity series was found to parallel that observed for the electrophilic aromatic substitutions and both series are supported by computational studies. As such, a reactivity scale was devised that showed that corannulene was less reactive than would be expected for an aromatic planar species of similar pi electron count.

Dialkyl Ether Formation by Nickel-Catalyzed Cross-Coupling of Acetals and Aryl Iodides

A new substrate class for nickel-catalyzed C(sp3) cross-coupling reactions is reported. α-Oxy radicals generated from benzylic acetals, TMSCl, and a mild reductant can participate in chemoselective cross-coupling with aryl iodides using a 2,6-bis(N-pyrazolyl)pyridine (bpp)/Ni catalyst. The mild, base-free conditions are tolerant of a variety of functional groups on both partners, thus representing an attractive C-C bond-forming approach to dialkyl ether synthesis. Characterization of a [(bpp)NiCl] complex relevant to the proposed catalytic cycle is also described.

Direct benzylic alkylation via Ni-catalyzed selective benzylic sp 3 C-O activation

This article demonstrates the first cross coupling of benzyl ether with Grignard reagents via Ni-catalyzed benzylic sp3 C-O activation with high efficiency and excellent chemoselectivity. Benzylic sp3 C-O and aryl sp2 C-O were differentiated, controlled by ligands. Copyright

Photosolvolysis of 11H-benzofluoren-11-ol in aqueous solution

The photosolvolysis of 11 H-benzolfluoren-11-ol (2), a 9-fluorenol derivative, has been studied in aqueous solution to test the hypothesis of enhanced photosolvolytic reactivity of these compounds.It is found that compared to the model compound, α-phenyl-2-naphthalenemethanol (3), 2 exhibited enhanced photosolvolytic reactivity.Quantum yields for photosolvolysis in aqueous alcohol solutions and steady-state and transient fluorescence studies are reported in neutral and acid solutions.The results further support the notion that an intrinsically accelerated photodehydroxylation step is associated with the formation of a 9-fluorenyl type carbocation intermediate (formally 4n? electrons).