35342-71-3

Upstream product

• 6738-06-3 phenylethynylmagnesium bromide 
• 14735-44-5 crotylzinc bromide 
• 536-74-3 phenylacetylene 
• 4440-01-1 lithium phenylacetylide 
• 4784-77-4 (E/Z)-crotyl bromide 
• 98-81-7 1-bromovinylbenzene 
• 66534-32-5 α,α-diisopropyl-β-methylhomoallylic alcohol 

Relevant academic research and scientific papers

Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

A new method for the preparation and control of dynamic σ-allylgalliums is disclosed. Upon treatment with a Grignard reagent and gallium trichloride, bulky homoallyl alcohols undergo gallium-mediated retro-allylation reaction to provide σ-allylgallium reagents. The σ-allylgallium reagents generated were applied to carbonyl allylation. The retro-allylation reaction generates (Z)- and (E)-σ-crotylgalliums stereospecifically, starting from erythro- and threo-homoallyl alcohols, respectively. The stereochemically defined crotylgallium reagents effected stereoselective allylation of aldehydes. Allylgallation reaction of alkynes with the allylgallium reagents prepared by retro-allylation is also described.

Palladium-catalyzed allyl cross-coupling reactions with in situ generated organoindium reagents

Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions, using allylindium generated in situ from allyl halides and indium, is demonstrated. Allylindium compounds may be effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions. A variety of allyl halides, such as allyl iodide, allyl bromide, crotyl bromide, prenyl bromide, geranyl bromide, and 3-bromocyclohexene afforded the allylic cross-coupling products in good to excellent yields. Stereochemistry of the double bond is retained in the allylic cross-coupling reactions. Electrophilic cross-coupling partners, such as aryl and vinyl halides, dibromoolefin, alkynyl iodide, and aryl and vinyl triflates participate in these reactions. The presence of various substituents, such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phenylamido, nitro, and chloride groups on the aromatic ring of electrophilic coupling partners showed little effect on the efficiency of the reactions. The present conditions work equally well for not only intermolecular but also intramolecular palladium-catalyzed cross-coupling reactions. These methods provide an efficient synthetic method for the introduction of an allyl group, which can be easily further functionalized to afford an sp2- and sp-hybridized carbon. The present method complements existing synthetic methods as a result of advantageous features such as easy preparation and handling, thermal stability, high reactivity and selectivity, operational simplicity, and low toxicity of allylindium reagents.

Highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles

This paper describes highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles such as aryl and vinyl triflates, vinyl halides, dibromoolefin, and alkynyl iodide. The reactions were carried out using 4 mol % Pd(PPh3)4 in the presence of 3 equiv of LiCl in DMF at 100 °C under a nitrogen atmosphere. Allylindium, generated from the reaction of 1 equiv of indium with 1.5 equiv of allyl halide, gave the best result as a coupling partner. The present method is mild and simple to apply, and it produces a diverse range of allylic compounds in good to excellent yields.