6301-50-4

Upstream product

• 78-77-3 Isobutyl bromide 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 30963-76-9 8-methylnonane-2,6-dione 
• 56671-81-9 3-bromo-2-cyclohexen-1-one 
• 598-30-1 sec.-butyllithium 
• 556813-33-3 tert-Butyl-dimethyl-{3-[2-methyl-prop-(Z)-ylidene]-cyclohex-1-enyloxy}-silane 
• 926-62-5 isobutylmagnesium bromide 
• 504-02-9 1,3-cylohexanedione 
• 930-68-7 cyclohexenone 
• 29179-03-1 (E)-3-(prop-1-en-1-yl)cyclohex-2-en-1-one 
• 75-16-1 methylmagnesium bromide 
• 5674-02-2 2-methylpropylmagnesium chloride 

Downstream Products

• 73959-39-4 (3R)-3-isobutylcyclohexanone 
• 1092571-64-6 (R)-3-phenyl-3-isobutylcyclohexanone 
• 1103917-47-0 3-isobutyl-3-propylcyclohexanone 
• 73959-38-3 (S)-3-isobutyl-cyclohexanone 
• 1186225-55-7 3-isobutyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexanone 
• 1199807-32-3 C₁₄H₂₆O 
• 1199807-31-2 (R)-3-isobutyl-3-propylcyclohexanone 
• 1240123-19-6 3-(diphenylphosphoryl)-3-isobutylcyclohexanone 
• 1309474-73-4 C₁₆H₂₈O 
• 1309474-30-3 (S)-(E)-3-(hex-1-enyl)-3-isobutylcyclohexanone 
• 1312208-24-4 (+)-(S)-3-isobutyl-3-(nitromethyl)cyclohexan-1-one 
• 1244782-96-4 3-isobutyl-3-(prop-1-en-2-yl)cyclohexanone 

Relevant academic research and scientific papers

Formation of quaternary stereogenic centers by NHC-Cu-catalyzed asymmetric conjugate addition reactions with Grignard reagents on polyconjugated cyclic enones

The copper-catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4-addition products. This reaction allows for the creation of all-carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining unsaturation on the 1,4 adducts give access to valuable synthetic transformations. Copyright

Formation of quaternary chiral centers by N-Heterocyclic carbene-CuCatalyzed asymmetric conjugate addition reactions with grignard reagents on trisubstituted cyclic enones

The copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclic enones allows the formation of all-carbon chiral quaternary centers. We demonstrate in this article that N-heterocyclic carbenes act as efficient chiral ligands for this transformation. High enantioselectivities (up to 96% ee) could be obtained for a variety of substrates.

Enantioselective hydrogenation of enones with a hydroformylation catalyst

Use of a typical rhodium precatalyst for hydroformylation results in the enantioselective hydrogenation of cyclic enones with up to 90% ee. Extensive screening of chiral ligands reveals the simple ligand Chiraphos as the best ligand, so far. The hydrogenation shows high chemoselectivity. Exclusive formation of saturated, chiral b-branched ketones is observed. It is proposed that the catalyst follows a frustrated hydroformylation pathway ("monohydride-based mechanism") and differs by that from the classical cationic Schrock-Osborn type rhodium precatalysts ("dihydride-based mechanism") for enantioselective hydrogenation. The catalyst operates under neat conditions and is easily recyclable by simply distilling off the reaction mixture and treatment with syn gas prior to hydrogenation.

Regiodivergent 1,4 versus 1,6 asymmetric copper-catalyzed conjugate addition

(Chemical Equation Presented) Metal matters: A highly regiodivergent copper-catalyzed asymmetric conjugate addition to α,β and γ,δ Michael acceptors is described. Zinc and aluminum reagents afford the 1,6 adduct with good to moderate enantioselectivity in the presence of ligand 1 (see scheme). In contrast, Grignard reagents used with hydroxy imidazolium ligand 2 afforded the 1,4 adduct with excellent ee values.

Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers

Me3Al, Et1Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3-CN)4]BF4 or [CuOTf]2· C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.

Highly enantioselective transfer hydrogenation of α,β- unsaturated ketones

We describe an efficient and highly enantioselective conjugate transfer hydrogenation of α,β-unsaturated ketones that is catalyzed by a salt made from tert-butyl valinate and a recently introduced powerful chiral phosphoric acid catalyst (TRIP). Copyright

Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers

Trimethyl- and triethylaluminum undergo enantioselective conjugate addition to 3-and 2-substituted cyclohexenones in the presence of catalytic amounts of a Cu salt and a phosphoramidite ligand L* (see scheme). Thus, chiral quaternary centers can be built with up to 96.6% ee. Functionalized enones lead to bicyclic structures by a subsequent aldol reaction.

Two methods for the preparation of 2-cyclohexenones from resin-bound 1,3-cyclohexanedione

The addition of organolithium or Grignard reagents to viny]ogous ester resin 1 followed by mild hydrolysis of product resins 2 provides 3-alkyl-2-cyclohexenones in high purity (>95%). Alternatively, conversion of 1 to vinyl triflate resin 4 followed by palladium-mediated couplings with aryl boronic acids and hydrolysis furnishes 3-ary]-2-cyclohexenones in lower yield, but exceptional purity.

Phosphoniosilylation: An Efficient and Practical Method for the β-Functionalization of Enones

A useful procedure for the β-functionalization of enones is described in which the Wittig reaction is combined with an initial phosphoniosilylation process.

Reaction of β-halo α,β-unsaturated ketons with cuprate reagents. Efficient syntheses of β,β-dialkyl ketones and β-alkyl α,β-unsaturated ketones. A synthesis of (Z)-jasmone

Treatment of the 3-halo-2-cyclohexen-1-ones 11-15 and 17 with an excess of lithium dimethylcuprate provided good to excellent yields of the corresponding 3,3-dimethylcyclohexanones 21-24.Similar reactions involving the β-bromo cyclopentenones 19 and 20 stopped at the monoaddition stage, producing the cyclopentenones 40 and 43.Reaction of the β-bromo cyclohexenones 12 and 15 with 1.1 equiv. of lithium dimethylcuprate did not effect clean conversion of these substrates into the corresponding 3-methyl-2-cyclohexen-1-ones.When a series of β-bromo enones 12, 14-19were allowed to react with the lithium (phenylthio)(alkyl)cuprates 44-47, the correspondig β-alkyl enones were, in general, produced cleanly and efficiently.However, reaction of 3-bromo-2-methyl-2-cyclopenten-1-one (19) with the cuprate reagent 44 gave mainly the β-phenylthio enone 49.This undesired result could be avoided by employing, in the place of 19, The β-iodo cyclopentenone 50, which reacted smoothly with 44 to give a high yield of 2,3-dimethyl-2-cyclopenten-1-one (40).Reaction of 3-bromo-2-cyclohexen-1-one (14) with 3 equiv. of the mixed vinylcuprate reagent 48 gave 3-(3-butenyl)-2-cyclohexen-1-one (32).Alkylation of 1,3-cyclopentanedione with (Z)-1-chloro-2-pentene afforded compound 51, which was converted into the β-bromo enone 52.Treatment of the latter substance with lithium dimethylcuprate provided (Z)-jasmone (53).