28017-81-4

Upstream product

• 108-86-1 bromobenzene 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 
• 92249-36-0 5,5-dimethyl-3-oxocyclohex-1-en-1-yl 4-nitrobenzenesulfonate 
• 126-81-8 dimedone 
• 108-90-7 chlorobenzene 

Downstream Products

• 76399-23-0 (E)-3-benzyl-5,5-dimethyl-2-cyclohexenylidene acetonitrile 
• 76399-22-9 (Z)-3-benzyl-5,5-dimethyl-2-cyclohexenylidene acetonitrile 

Relevant academic research and scientific papers

Ligand Control of Palladium-Catalyzed Site-Selective α- and γ-Arylation of α,β-Unsaturated Ketones with (Hetero)aryl Halides

This study describes the first palladium-catalyzed, site-selective α- and γ-arylation of α,β-unsaturated ketones with (hetero)aryl halides. A wide range of hetero(aryl)halides coupled with α,β-unsaturated ketones, and transformation into the arylated products proceeded with excellent to good yields. The site selectivity of the reaction is switchable by simply changing the phosphine ligand to access either α-arylated or γ-arylated products in good to excellent yields by using a low catalyst loading, and the method demonstrates good functional-group compatibility.

Handy Protocols using Vinyl Nosylates in Suzuki-Miyaura Cross-Coupling Reactions

Vinyl nosylates derived from 1,3-dicarbonyl compounds could be engaged in Suzuki-Myaura cross coupling reactions with aryl-, vinyl- and methylboronic acids or trifluoborate derivatives at room temperature in the presence of 2mol% of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) [PdCl2(dppf)]. One-pot procedures have been set up for practical and efficient nosylation-cross-coupling reactions. Nosylate, as a cheap novel pseudo-halide, gives very stable compounds and is very efficient in Suzuki-Myaura cross coupling reactions (21 examples, 44-99%).

Regioselective arylation on the γ-position of α, β-unsaturated carbonyl compounds with aryl bromides by palladium catalysis

Arylation of 2-substituted 2-alkenals and 3-substituted 2-cyclohexen- and 2-cyclopenten-1-ones can effectively and regioselectively proceed at their γ-position by treatment with aryl bromides in the presence of a palladium catalyst and a base.

Arynic Condensations of Ketone Enolates. 15. New Synthetic Applications of the Condensation of α,β-Unsaturated Ketone Enolates on Benzyne

Arynic condensations of both cyclic and acyclic α,β-unsaturated ketone enolates are studied.First, condensation of substituted cyclohexenone enolates with benzyne leads to a new class of cyclobutanic alcohols 6.Ring opening of 6 under basic conditions is described as a good means of synthesizing benzocyclooctadienones 10 and 19, and, in appropriate cases, benzocyclooctenediones of type 12.Thermal dehydration of 6 affords 1,3-disubstituted naphthalenes in good yields.Second, condensations of a few acyclic α,β-unsaturated ketone enolates with benzyne are shown to be of synthetic usefulness; depending on the substituents on both sides of the carbonyl group, these condensations may lead either to substituted naphthalenes or to phenyl ketones or tetralones.