62179-16-2

Upstream product

• 1889-20-9 n-butylmagnesium iodide 
• 111155-52-3 (E)-1-acetyl-4-(phenyloxy)-2-butene 
• 693-03-8 n-butyl magnesium bromide 
• 2442-10-6 oct-1-en-3-yl acetate 
• 108-95-2 phenol 
• 3913-80-2 (E)-2-octen-1-yl acetate 
• 15972-89-1 (E)-1-phenoxy-2,7-octadiene 

Relevant academic research and scientific papers

Biodegradable ionic liquids: Selected synthetic applications

3-Methyl-1-(propyloxycarbonylmethyl)imidazolium octylsulfate 1a and 3-methyl-1-(pentyloxycarbonylmethyl)imidazolium octylsulfate 2a are ionic liquids that have previously been shown to be readily biodegradable in the CO2 headspace test (ISO 14593). In the present study, these ionic liquids were evaluated as reaction media for Diels?Alder and hydrogenation reactions. The comparison of the performance of these two designer solvents in these reactions with those conducted in other, non-biodegradable ionic liquids has demonstrated that they are comparable and viable solvents. CSIRO 2007.

Asymmetric induction in the arenethiolatocopper(I)-catalyzed substitution reaction of Grignard reagents with allylic substrates

The influence of some experimental parameters on the regio- and enantioselectivity in the 'γ-selective substitution reaction of Grignard reagents RMgX with acyclic allylic acetates catalyzed by the arenethiolatocopper(I) complex (S)-1 was studied. When more bulky arenethiolatocopper(I) complexes than (S)-1 were employed in a reaction of allylic acetate 3 with n-BuMgI, the enantioselectivities observed for the γ- product were lower. With an arenethiolatocopper(I) catalyst prepared in situ, several Grignard reagents were studied in a substitution reaction with acetate 2. Compared to n-BuMgI, more bulky Grignard reagents gave no improvement of the enantioselectivity in the formation of the γ-product. (C) 2000 Elsevier Science Ltd.

Chiral Arenethiolatocopper(I) Catalyzed Substitution Reactions of Acyclic Allylic Substrates with Grignard Reagents.

Asymmetric induction can be achieved in the γ-selective substitution reaction of allylic substrates (R'CH=CH-CH2Y) with n-BuMgI catalyzed by the chiral arenethiolatocopper(I) complex 1b.It was found that the enantiomeric excess of the γ-substituted product (R'CH(n-Bu)CH=CH2) is influenced by the coordinating ability of the leaving group Y, and e.e.'s of up to 42percent (R'=Cy, Y=OAc) have been obtained.

ortho-Chelating Arenethiolatocopper(I) Complexes as Versatile Catalysts in the Regioselective Cross-Coupling of Allylic Derivatives with nBuMgI - An Example of Reversed Reactivity of Leaving Groups

The regioselectivity in the arenethiolactocopper(I)-catalyzed cross-coupling reaction of allylic substrates was studied.It was found that allylic acetates gave highly γ-selective reactions in Et2O at 0 deg C with slow addition of the Grignard reagent, whereas α-selective reactions were obtained in THF at -30 deg C with fast addition of the Grignard reagent.It is proposed that the formation of an intermediate in Et2O, in which the allylic acetate coordinates in a bidentate fashion to the arenethiolatocopper(I) catalyst, dramatically increases the reactivity of the leaving group and results in excellent γ-selectivity.The remarkable observation that an allylic acetate can be made more reactive than an allylic chloride by using the arenethiolatocopper(I) catalyst 1a supports the theory of a bidentate coordination of the substrate to the catalyst through its double bond and acetate oxygen. - Keywords: allylic substrates . carbon-carbon coupling . catalysis . copper compounds

The Use of Ortho-Chelating Arenethiolate Non-transferable Groups in the Copper(I) Catalyzed Selective α or γ Substitution of Acyclic Allylic Substrates with Grignard Reagents

Ortho-amino arenethiolatocopper(I) compounds are excellent catalysts for the cross-coupling reaction of Grignard reagents with acylic allylic substrates.For example, reaction of n-BuMgI with geranyl acetate in Et2O at 0 deg C yields quantitatively the γ substitution product, whereas the same reaction in THF at -30 deg C affords selectively the α substitution product.

The use of metal reagents in stereo- and regioselective functionalizations of conjugated dienes

Conjugated dienes have been selectively functionalized via 1-acetoxy-4-chloro-2-alkenes and via 2-(phenylsulfonyl)-1,3-dienes.In both these approaches nucleophiles can be added to the 1- and 4-positions.It was shown that also non-stabilized carbon nucleophiles (from cuprates or copper(I)-catalyzed Grignard reactions) can be used.The utility of the functionalizations was demonstrated by the syntheses of a marine natural product and a butterfly pheromone.Finally, the 2-(phenyl-sulfonyl)-1,3-dienes show a dual electron demand in Diels-Alder reactions and give cycloadducts with both electron-rich and electron-deficient olefins.

"PALLADIUM COMPLEXES-KF / ALUMINA" CATALYSED EXCHANGE OF ALLYLIC GROUPS OF ESTERS WITH PHENOL

In the presence of KF/alumina and catalytic amounts of palladium complexes, phenol reacts with allylic esters under mild conditions to give the corresponding allyl phenyl ethers.

A Dual Regiocontrol in the Copper-catalysed Grignard Reaction with Primary Allylic Acetates

The reaction of primary allylic acetates with Grignard reagents in the presence of catalytic amounts of Li2CuCl4 can be regiochemically controlled to give either α- or γ-substitution of the allylic acetoxy group.