138832-46-9

Upstream product

• 106-95-6 allyl bromide 
• 163332-59-0 (3-Methoxy-cyclohex-1-enesulfonyl)-benzene 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 2622-05-1 allylmagnesium bromide 
• 1730-25-2 allylmagnesium bromide 
• 65995-76-8 1-allylcyclohex-2-en-1-ol 
• 65825-82-3 3-(Phenylsulfonyl)cyclohex-2-en-1-ol 
• 556-56-9 allyl iodid 
• 56671-82-0 3-Iodocyclohex-2-enone 

Downstream Products

• 29179-03-1 (E)-3-(prop-1-en-1-yl)cyclohex-2-en-1-one 
• 69016-40-6 3-allylcyclohex-2-en-1-ol 
• 645421-46-1 pent-4-enoic acid 3-allyl-cyclohex-2-enyl ester 
• 645421-61-0 [(E)-1-(3-Allyl-cyclohex-2-enyloxy)-penta-1,4-dienyloxy]-triisopropyl-silane 
• 1097631-12-3 3-allyl-1-butylcyclohex-2-en-1-ol 
• 1431136-79-6 (2S,3R)-2,3-epoxy-3-allylcyclohexanone 

Relevant academic research and scientific papers

Palladium-Mediated Remote Functionalization in γ- And ?-Arylations and Alkenylations of Unblocked Cyclic Enones

We report herein an extensive investigation of simple and regioselective endo- as well as exo-γ-arylations of silyl-dienol ethers of unblocked cyclic enones with the utilization of palladium-catalyzed, modified Kuwajima-Urabe conditions. We have also successfully explored a new exo-?-arylation of silyl-trienol ethers of π-extended cyclic enones. In addition, we also report, herein, exclusive γ- and ?-alkenylation of silyl-dienol and silyl-trienol ethers of cyclic enones.

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.).

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.

The cinchona primary amine-catalyzed asymmetric epoxidation and hydroperoxidation of α,β-unsaturated carbonyl compounds with hydrogen peroxide

Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz-Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5-15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure-activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations.

Palladium-catalyzed allyl cross-coupling reactions with in situ generated organoindium reagents

Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions, using allylindium generated in situ from allyl halides and indium, is demonstrated. Allylindium compounds may be effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions. A variety of allyl halides, such as allyl iodide, allyl bromide, crotyl bromide, prenyl bromide, geranyl bromide, and 3-bromocyclohexene afforded the allylic cross-coupling products in good to excellent yields. Stereochemistry of the double bond is retained in the allylic cross-coupling reactions. Electrophilic cross-coupling partners, such as aryl and vinyl halides, dibromoolefin, alkynyl iodide, and aryl and vinyl triflates participate in these reactions. The presence of various substituents, such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phenylamido, nitro, and chloride groups on the aromatic ring of electrophilic coupling partners showed little effect on the efficiency of the reactions. The present conditions work equally well for not only intermolecular but also intramolecular palladium-catalyzed cross-coupling reactions. These methods provide an efficient synthetic method for the introduction of an allyl group, which can be easily further functionalized to afford an sp2- and sp-hybridized carbon. The present method complements existing synthetic methods as a result of advantageous features such as easy preparation and handling, thermal stability, high reactivity and selectivity, operational simplicity, and low toxicity of allylindium reagents.

Stereoselective aziridination of cyclic allylic alcohols using chloramine-T

The stereoselective aziridination of a range of cyclic allylic alcohols using two different chloramine salts (4-MeC6H4SO 2NClNa, TsNClNa and t-BuSO2NClNa, BusNClNa) has been explored. The stereoselectivity of these reactions was highly dependent on the structure of the allylic alcohol and the chloramine salt. Generally, mixtures of cis- and trans-hydroxy aziridines were obtained, in which the major diastereomer was the cis-hydroxy aziridine, whilst complete cis- diastereoselectivity was observed in the aziridination of 1,3-disubstituted allylic alcohols. In each case studied, aziridination using BusNClNa gave higher cis-stereoselectivity than that observed for the same reaction using TsNClNa. Unexpectedly, application of the aziridination conditions to 1-substituted cyclopen-2-en-1-ols did not generate the aziridines. Instead, epoxy sulfonamides were obtained.

Highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles

This paper describes highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles such as aryl and vinyl triflates, vinyl halides, dibromoolefin, and alkynyl iodide. The reactions were carried out using 4 mol % Pd(PPh3)4 in the presence of 3 equiv of LiCl in DMF at 100 °C under a nitrogen atmosphere. Allylindium, generated from the reaction of 1 equiv of indium with 1.5 equiv of allyl halide, gave the best result as a coupling partner. The present method is mild and simple to apply, and it produces a diverse range of allylic compounds in good to excellent yields.