123732-13-8

Upstream product

• 56671-82-0 3-Iodocyclohex-2-enone 
• 623-00-7 4-bromobenzenecarbonitrile 
• 131379-14-1 4-cyanophenylzinc bromide 
• 109-72-8 n-butyllithium 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 930-68-7 cyclohexenone 
• 126747-14-6 4-cyanophenylboronic acid 
• 412044-48-5 (4-cyanophenyl)magnesium bromide 

Downstream Products

• 537708-77-3 3-(4-cyanophenyl)-3-phenylcyclohexanone 
• 537708-78-4 5-(4-cyanophenyl)-5-phenylcyclohex-2-enone 
• 537708-80-8 3-tert-butyl-5-(4-cyanophenyl)-5-phenylcyclohex-2-enone 
• 486455-27-0 3'-hydroxybiphenyl-4-carbonitrile 
• 149505-72-6 3'-aminobiphenyl-4-carbonitrile 
• 1453494-28-4 C₁₃H₁₂N₂O 

Relevant academic research and scientific papers

A highly efficient metal-free approach to: Meta - And multiple-substituted phenols via a simple oxidation of cyclohexenones

A novel and efficient metal-free approach to substituted phenols has been disclosed from simple and readily available cyclohexenones and cyclohexenone equivalents. Dimethyl sulfoxide (DMSO), a simple and common organic reagent, was employed as a mild oxidant in this I2-catalysis, which significantly tolerates various substituents including some easily oxidizable or reducible functionalities. The challenging meta- and multiple-substituted phenols could be well prepared by this method. The metal-free and mild oxidation make this protocol very simple, practical, and easy to handle.

Stereoselective preparation of polyfunctional alkenylindium(III) halides and their cross-coupling with unsaturated halides

The direct insertion of indium powder to cycloalkenyl iodides in the presence of LiCl in THF allows the preparation of new highly functionalized cycloalkenylindium(III) derivatives. In addition, we discovered that, in contrast to many metal insertions to alkenyl iodides which proceed with a loss of stereochemistry, the insertion of In/LiCl to stereodefined (Z)- and (E)-styryl iodides in THF proceeded with high retention of stereochemistry. After a palladium-catalyzed cross-coupling, various polyfunctionalized (Z)- and (E)-stilbenes were obtained with high stereoselectivity.

Aerobic oxidative heck/dehydrogenation reactions of cyclohexenones: Efficient access to meta-substituted phenols

Jockeying for the (meta)position: A new dicationic palladium(II) catalyst, employing a 6,6′-dimethyl-2,2′-bipyridine ligand, promotes both the aerobic oxidative Heck coupling and dehydrogenation reactions of cyclohexenones. These reactions may be combined in a one-pot sequence to enable the straightforward synthesis of meta-substituted phenols (see scheme). Copyright

Functionalized alkenylzinc reagents bearing carbonyl groups: Preparation by direct metal insertion and reaction with electrophiles

Highly functionalized cyclic and acyclic alkenylzinc reagents bearing functional groups such as aldehyde, keto, and ester groups were readily prepared by either direct zinc insertion in the presence of LiCl or by magnesium insertion in the presence of LiC

Addition reaction of arylboronic acids to aldehydes and α,β-unsaturated carbonyl compounds catalyzed by conventional palladium complexes in the presence of chloroform

Arylboronic acids react with aldehydes and α,β-unsaturated carbonyl compounds in the presence of a base and a catalytic amount of a palladium(0) complex with chloroform, affording the corresponding addition products in good yields, and chiral benzhydrol was obtained with up to 43% e.e. using (S,S)-bppm as a ligand. General palladium complexes have no catalytic activity without chloroform. Because chloroform is essential for this reaction, these reactions would be promoted by dichloromethylpalladium(II) species.

An experimental and theoretical study of the type C enone rearrangement: Mechanistic and exploratory organic photochemistry

We recently described a new photochemical rearrangement which we termed a Type C process. The reaction involves a δ to α aryl migration in 5-disubstituted cyclohexenones also having bulky C-3 substituents. In contrast to most cyclohexenone rearrangements, the reaction occurs via a twisted π-π* excited triplet rather than the usual n-π* state. The electronic nature of the rearrangement was assessed using migration selectivity with p-anisyl and p-cyanophenyl groups. A synthesis of the reactants was elaborated, and the product structures were established by X-ray and NMR analysis. The reaction mechanism was established further with DFT and CASSCF computations. In the latter, localized NBO basis orbitals permitted proper selection of the active space. The nature of the diradical intermediates as well as the transition states was established computationally. Sensitization experiments with regioselectivities the same as those in direct irradiation confirmed the triplet multiplicity of the process.

Palladium catalyzed cross-couplings of organozincs in ionic liquids

Negishi cross-coupling reactions between aryl- or benzylzinc halides and various aryl iodides smoothly occur in ionic liquids in the presence of the new ionic phosphine ligand 2. This solvent allows a facile work-up and rapid cross-coupling reactions at r

Preparation of polyfunctional aryl and alkenyl zinc halides from functionalized unsaturated organolithiums and their reactivity in cross-coupling and conjugated addition reactions

Functionalized aryl and alkenyl iodides undergo an iodine-lithium exchange at -90 to -80°C providing polyfunctional organolithiums which are stable for a short time at these low temperatures and can be transmetalated to organozinc derivatives by the addition of zinc bromide. The resulting unsaturated organozinc halides can then be warmed up and are perfectly stable at 25°C. They react directly with tosyl cyanide. In the presence of CuCN·2LiCl, they add in a Michael-fashion to alkylidenemalonates. In the presence of catalytic amounts of Pd(dba)2 and TPP or TFP, they undergo readily a cross-coupling at 25°C with aryl and alkenyl iodides. The Pd-catalyzed coupling of arylzinc bromides with aryl triflates could also be achieved by using dppf as a ligand and 60°C as reaction temperature.