5277-36-1

Usage

InChI:InChI=1/C12H18O/c1-3-8-12(9-4-2)10-6-5-7-11(12)13/h3-4H,1-2,5-10H2

Upstream product

• 94-66-6 2-allylcyclohexan-1-one 
• 107-18-6 allyl alcohol 
• 15022-08-9 diallylcarbonate 
• 5453-93-0 allyl 2-oxocyclohexane-1-carboxylate 
• 108-94-1 cyclohexanone 
• 92954-34-2 N,N'-dicyclohexyl-O-allylisourea 
• 60-29-7 diethyl ether 
• 86950-86-9 allyl cyclohex-1-en-1-yl carbonate 
• 53608-84-7 1,1-bis-(2-propenyloxy)-cyclohexane 
• 79643-88-2 1-(2-propen-1-yloxy)cyclohexene 
• 106-95-6 allyl bromide 
• 18709-01-8 2-hydroxycyclohex-1-enecarboxylic acid 
• 81112-28-9 methyl 2-methylprop-2-enyl carbonate 
• 88419-71-0 2-Allyloxycarbonyloxy-cyclohex-1-enecarboxylic acid allyl ester 

Downstream Products

• 92729-22-1 2,2,6-triallyl-cyclohexanone 
• 92775-13-8 (R)-2,2-Diallyl-1-methyl-cyclohexanol 
• 23438-68-8 7aβ-Hydroxy-2-methyl-3aα-allyl-perhydrobenzofuran 
• 23438-68-8 7aα-Hydroxy-2-methyl-3aα-allyl-perhydrobenzofuran 
• 500548-27-6 2,2-dipropyl-cyclohexanone 

Relevant academic research and scientific papers

Organic Compounds

Described are spiroalkyl- and -alkenylketones and esters thereof, a method for their production and fragrance compositions comprising them.

Palladium-catalyzed decarboxylative asymmetric allylic alkylation of enol carbonates

Palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) of allyl enol carbonates as a highly chemo-, regio-, and enantioselective process for the synthesis of ketones bearing either a quaternary or a tertiary R-stereogenic center has been investigated in detail. Chiral ligand L4 was found to be optimal in the DAAA of a broad scope of cyclic and acyclic ketones including simple aliphatic ketones with more than one enolizable proton. The allyl moiety of the carbonates has been extended to a variety of cyclic or acyclic disubstituted allyl groups. Our mechanistic studies reveal that, similar to the direct allylation of lithium enolates, the DAAA reaction proceeds through an "outer sphere" S N2 type of attack on the π-allylpalladium complex by the enolate. An important difference between the DAAA reaction and the direct allylation of lithium enolates is that in the DAAA reaction, the nucleophile and the electrophile were generated simultaneously. Since the π-allylpalladium cation must serve as the counterion for the enolate, the enolate probably exists as a tight-ion-pair. This largely prevents the common side reactions of enolates associated with the equilibrium between different enolates. The much milder reaction conditions as well as the much broader substrate scope also represent the advantages of the DAAA reaction over the direct allylation of preformed metal enolates.

DIRECT Α-ALLYLATION OF KETONES WITH O-ALLYLISOUREA CATALYZED BY PALLADIUM(0)

Direct α-allylation of ketones catalyzed by a palladium(0)-diphosphine system took place employing O-allylisourea as the allylating reagent under neutral conditions ar room temperature in DMF.

PALLADIUM-CATALYZED SYNTHESIS OF α,β-UNSATURATED KETONES FROM KETONES VIA ALLYL ENOL CARBONATES

Allyl enol carbonates, prepared by quenching ketone enolates with allyl chloroformate, are converted to α,β-unsaturated ketones with Pd(OAc)2-dppe catalyst in CH3CN.

A NEW ONE-POT METHOD FOR α,α-DIALLYLATION OF KETONES BASED ON THE PALLADIUM-CATALYZED REACTION OF ALLYLIC CARBONATES AND ALLYL β-KETO CARBOXYLATES UNDER NEUTRAL CONDITIONS

A new method for α,α-diallylation of ketones catalyzed by palladium-phosphine complexes under neutral conditions has been developed.Allylation of β-keto carboxylates with allylic carbonates, followed by the decarboxylation-allylation as a one-pot reaction affords diallylated ketones in good yields.

Specific Two-Step Decarboxylation of Copper(I,II) β-Keto Carboxylates. A Novel Type of Regulation of the Decarboxylation of β-Keto Acids

Copper(I,II) β-keto carboxylates undergo a specific two-step decarboxylation.For example, the decarboxylation of copper(I) 1-oxocyclohexane-2-carboxylate (1) evolves CO2 in a 50percent yield in dimethylformamide (DMF) at 70 deg C.No further CO2 evolution beyond this 50percent decarboxylation occurs at 70 deg C.At a higher temperature of 120 deg C., the remaining 50percent of the CO2 is released.This specific two-step decarboxylation of 1 results from the intermediate formation of a dicopper(I) salt of the enol of 1-oxocyclohexane-2-carboxylic acid (10) which is stable to decarboxylation at 70 deg C.Compound 10 is isolated from the reaction mixture after the 50percent decarboxylation.Decarboxylations of copper(I,II) benzoylacetates, copper(I) oxaloacetate, copper(II) 1-oxo-cyclohexane-2-carboxylate, and copper(II) chloride 1-oxocyclohexane-2-carboxylate also proceed stepwise in DMF.On the other hand, copper(I,II) benzoylcyclopropane-1-carboxylates without an enolizable α-hydrogen atom evolve CO2 in a usual one-step manner.The present specific two-step decarboxylation of copper(I,II) β-keto carboxylates provides a novel type of regulation of the decarboxylation of β-keto acids and also a method of generating copper(I,II) enolate.The bearing of the two-step decarboxylation of copper(I) β-keto carboxylates on both the Cu(I)-mediated carboxylation of ketones and organic synthesis is also described.