80359-96-2

Upstream product

• 80359-83-7 methyl isopropyl ketone diethyl acetal 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 5650-76-0 isobutyrylacetic acid 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 673-32-5 1-Phenylprop-1-yne 
• 17510-45-1 2-(trimethylsilyloxy)-3-methyl-1-butene 
• 40595-34-4 (E)-trimethyl(3-phenylallyl)silane 

Relevant academic research and scientific papers

Tandem Rh-catalysis: Decarboxylative β-keto acid and alkyne cross-coupling

Herein, we describe a regioselective Rh-catalyzed decarboxylative cross-coupling of β-keto acids and alkynes to access branched γ,δ-unsaturated ketones. Rh-hydride catalysis enables the isomerization of an alkyne to generate a metal-allyl species that can undergo carbon-carbon bond formation. Ketones are generated under mild conditions, without the need for base or activated electrophiles.

Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes

A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

Iridium-catalyzed regioselective decarboxylative allylation of β-ketoacids: Efficient construction of γ,δ-unsaturated ketones

A highly regioselective protocol for the direct synthesis of γ,δ-unsaturated ketones from β-ketoacids and allylic alcohols was proposed and accomplished relying on the combination of [Ir(cod)Cl]2 and 10-camphorsulfonic acid via decarboxylative allylation.

Versatile Desilylative Cross-Coupling of Silyl Enol Ethers and Allylic Silanes via Oxovanadium-Induced Chemoselective One-Electron Oxidation

The chemoselective cross-coupling of silyl enol ethers and allylic silanes to γ,δ-unsaturated ketones is achieved by the oxovanadium(V)-induced oxidative desilylation of the more readily oxidizable organosilicon compounds.

Ketal Claisen Rearrangements of Simple Aliphatic Ketals

The ketal Claisen rearrangement has been studied with eight simple unsymmetrical ketals in order to establish the regioselectivity associated with the transformation.Three different allylic alkohols were examined.Carbon-carbon bond formation on the more highly substituted branch of the parent ketone generally predominated over substitution on the less highly substituted branch.However, additional substituents on the α or β carbons of the ketal lower the selectivity substantially.Extensive β substitution can completely reverse the normal selectivity.The rection is relatively insensitive to the concentration of the weak acid catalyst.The yields range between 27 and 84 percent, and the products have been characterized.A model that accounts for the observations is also described.

Regioselectivity of the Ketal Claisen Rearrangement

The ketal Claisen rearrangement with a simple unsymmetrical ketal exhibits a high degree of regioselectivity, which is attenuated by substitution of the α- and β-carbon atoms of the ketal.