60174-90-5

Upstream product

• 930-68-7 cyclohexenone 
• 99354-16-2 phenylcerium dichloride 
• 591-51-5 phenyllithium 
• 100-59-4 phenylmagnesium chloride 
• 113811-12-4 2⁽⁶⁾Li⁽¹⁺⁾*Cu⁽¹⁺⁾*3C₆H₅^(1-)=(C₆H₅)3Cu⁽⁶⁾Li₂ 
• 100-58-3 phenylmagnesium bromide 
• 108-86-1 bromobenzene 
• 51608-60-7 N-(benzylidene)-p-methylbenzenesulfonamide 

Downstream Products

• 15619-34-8 1-(cyclohexa-1,5-dienyl)benzene 
• 1206544-13-9 2-methyl-5-(3-phenylcyclohex-2-enyl)furan 
• 1234577-24-2 benzyl (RS)-(3-phenylcyclohex-2-en-1-yl)carbamate 
• 1253739-36-4 (R)-3-phenyl-2-cyclohexen-1-yl acetate 
• 1335129-10-6 1-(3-allyloxycyclohex-1-enyl)benzene 
• 191100-10-4 1-(3-isopropoxycyclohex-1-enyl)benzene 
• 1335129-09-3 1-(3-tert-butoxycyclohex-1-enyl)benzene 
• 1357476-11-9 2,4-dimethyl-6-(3-phenylcyclohex-2-enyl)benzenamine 
• 10345-87-6 3-phenylcyclohex-2-enone 
• 17488-64-1 3-phenyl-cyclohex-2-enol 
• 1395414-77-3 3-phenyl-1-(1-propyloxy)-2-cyclohexene 
• 1647159-53-2 1-trifluoromethylthio-1-phenyl-cyclohex-2-ene 
• 1034192-76-1 2,3-dibromo-1-phenylcyclohexanol 
• 15619-32-6 1-phenyl-cyclohexa-1,3-diene 

Relevant academic research and scientific papers

Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost of Benzotriazoles with 1,3-Dienes

The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, bec

Lewis acids promoted 3 + 2 cycloaddition of oxaziridines and cyclic allylic alcohols through carbonyl imine intermediates

Syntheses of isoxazolidines through the carbonyl imine intermediates are currently limited to monosubstituted olefin substrates. Herein, we reported syntheses of novel bicyclic isoxazolidine-containing compounds through 1,3-dipolar cycloaddition reactions

Chemo-Enzymatic Oxidative Rearrangement of Tertiary Allylic Alcohols: Synthetic Application and Integration into a Cascade Process

A chemo-enzymatic catalytic system, comprised of Bobbitt's salt and laccase from Trametes versicolor, allowed the [1,3]-oxidative rearrangement of endocyclic allylic tertiary alcohols into the corresponding enones under an Oxygen atmosphere in aqueous media. The yields were in most cases quantitative, especially for the cyclopent-2-en-1-ol or the cyclohex-2-en-1-ol substrates without an electron withdrawing group (EWG) on the side chain. Transpositions of macrocyclic alkenols or tertiary alcohols bearing an EWG on the side chain were instead carried out in acetonitrile by using an immobilized laccase preparation. Dehydro-Jasmone, dehydro-Hedione, dehydro-Muscone and other fragrance precursors were directly prepared with this procedure, while a synthetic route was developed to easily transform a cyclopentenone derivative into trans-Magnolione and dehydro-Magnolione. The rearrangement of exocyclic allylic alcohols was tested as well, and a dynamic kinetic resolution was observed: α,β-unsaturated ketones with (E)-configuration and a high diastereomeric excess were synthesized. Finally, the 2,2,6,6-tetramethyl-1-piperidinium tetrafluoroborate (TEMPO+BF4?)/laccase catalysed oxidative rearrangement was combined with the ene-reductase/alcohol dehydrogenase cascade process in a one-pot three-step synthesis of cis or trans 3-methylcyclohexan-1-ol, in both cases with a high optical purity. (Figure presented.).

Preparation of optically active cycloalkenes bearing all-carbon quaternary stereogenic centres: Via lipase-oxovanadium combo-catalysed dynamic kinetic resolution

In this study, a novel asymmetric synthesis of all-carbon quaternary stereogenic centres is developed by the connection of three prochiral or achiral components - conjugated enones, organometallic compounds and vinyl esters - at the C-1 position of the enones. This method involves three sequential steps: 1,2-nucleophilic addition of an organometallic compound to the enone, lipase-catalysed dynamic kinetic resolution (DKR) of the tert-allylic alcohol and the Ireland-Claisen rearrangement of the optically active allyl ester thus generated. This method features the effective use of acyl moieties installed by DKR for achieving high atom economy. The application of this method to the protective-group-free asymmetric total synthesis of (-)-crinane, a core structure of a class of natural alkaloids, has demonstrated that it can alter a known synthetic pathway of a racemate into an asymmetric synthesis of an optically pure molecule while reducing the total transformation steps and increasing the overall yield. With these advantages, this method is practical and attractive as a new environmentally benign protocol.

Iodine-Promoted Metal-Free Aromatization: Synthesis of Biaryls, Oligo p-Phenylenes and A-Ring Modified Steroids

We describe efficient procedures based on the use of iodine for the synthesis of biaryls from arylcyclohexenols or arylcyclohexanols using sub-stoichiometric/catalytic iodine and dimethyl sulfoxide (DMSO) as oxidant. Heteroarylcyclohexanols also produced the corresponding biaryl products. It was proven that biphenyl can also be efficiently obtained when the quantity of iodine was reduced to 0.05 equiv. The method is compatible with different functional groups in the aromatic ring (either electron-donating or electron-withdrawing groups). For substrate scope, apart from cyclohexanone and cyclohexenone, some substituted cyclohexanones were also used to synthesize the starting arylcyclohexanols. The process was applied to the synthesis of oligo p-phenylenes and A-ring aromatized steroids, where the combined use of I2/DMSO not only provoked the necessary migration of the methyl group at C-10, but also further extended the conjugation.

Catalytic olefin hydroamination with aminium radical cations: A photoredox method for direct C-N bond formation

While olefin amination with aminium radical cations is a classical method for C-N bond formation, catalytic variants that utilize simple 2° amine precursors remain largely undeveloped. Herein we report a new visible-light photoredox protocol for the intramolecular anti-Markovnikov hydroamination of aryl olefins that proceeds through catalytically generated aminium radical intermediates. Mechanistic studies are consistent with a process involving amine oxidation via electron transfer, turnover-limiting C-N bond formation, and a second electron transfer step to reduce a carbon-centered radical, rendering the overall process redox-neutral. A range of structurally diverse N-aryl heterocycles can be prepared in good to excellent yields under conditions significantly milder than those required by conventional aminium-based protocols.

Palladium-catalyzed oxidative rearrangement of tertiary allylic alcohols to enones with oxygen in aqueous solvent

A one-pot procedure for Pd(TFA)2-catalyzed 1,3-isomerization of tertiary allylic alcohols to secondary allylic alcohols followed by a Pd(TFA)2/neocuproine-catalyzed oxidative reaction to β-disubstituted-α,β-unsaturated kenones was developed. (Chemical Equation Presented).

Migratory dynamic kinetic resolution of carbocyclic allylic alcohols

A novel migratory dynamic kinetic resolution based on the interplay between an enzyme acylation catalyst and a heterogeneous Bronsted acid as an isomerization/racemization catalyst gives rise to carbocyclic allylic esters with excellent stereoselectivity

Continuous flow-processing of organometallic reagents using an advanced peristaltic pumping system and the telescoped flow synthesis of (E/Z)-tamoxifen

A new enabling technology for the pumping of organometallic reagents such as n-butyllithium, Grignard reagents, and DIBAL-H is reported, which utilises a newly developed, chemically resistant, peristaltic pumping system. Several representative examples of its use in common transformations using these reagents, including metal-halogen exchange, addition, addition-elimination, conjugate addition, and partial reduction, are reported along with examples of telescoping of the anionic reaction products. This platform allows for truly continuous pumping of these highly reactive substances (and examples are demonstrated over periods of several hours) to generate multigram quantities of products. This work culminates in an approach to the telescoped synthesis of (E/Z)-tamoxifen using continuous-flow organometallic reagent-mediated transformations.

TARTROL-derived chiral phosphine-phosphite ligands and their performance in enantioselective Cu-catalyzed 1,4-addition reactions

By using (R,R,R,R)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane-5,6-bis- diphenylmethanol (TARTROL) as a chiral building block, a set of six modular phosphine-phosphite ligands (with a 1,2-phenylene backbone) were synthesized and evaluated in the Cu-catalyzed a