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Upstream product

• 36971-15-0 3-isopropyl-2-methyl-hex-5-en-3-ol 
• 768-60-5 4-methoxyphenylacetylen 
• 106-95-6 allyl bromide 
• 2632-13-5 2-Bromo-4'-methoxyacetophenone 
• 41448-64-0 1-(2,2-dichlorovinyl)-4-methoxybenzene 

Relevant academic research and scientific papers

Regioselective allylgallation of terminal alkynes

The reactions of terminal alkynes with allylgallium reagents generated in situ from gallium and allyl bromides gave the corresponding 1,4-dienes in good yield via Markovnikov addition in THF at 70°C. The Royal Society of Chemistry 2005.

Applications of allylsamarium bromide as a grignard reagent and a singleelectron transfer reagent in the one-pot synthesis of dienes and trienes

The utility of allylsamarium bromide, both as a nucleophilic reagent and a single-electron transfer (SET) reagent in the reaction of α-halo, γ-halo-αβ-unsaturated ketones and esters with allylsamarium bromide is reported for the first time in this paper. From a synthetic point of view, a general, efficient and experimentally simple one-pot method for the preparation of 1,4-dienes and trienes is developed. A possible mechanism of the transformation is proposed.

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.

Allyl- And Benzylindium Reagents. Carboindation of Carbon-Carbon and Carbon-Nitrogen Triple Bonds

The reaction of unactivated simple terminal alkynes 1 with allylindiums in THF proceeded smoothly to give the corresponding allylation products 2 in good to high yields. This result is in marked contrast to that of the reaction carried out in DMF, where the allylation of unactivated alkynes was very sluggish. The allylic group of the reagent was attached to the internal carbon of the triple bond, and indium was attached to the less substituted terminal carbon, except for the case of TMS substituted acetylenes 1j and 1k in which the allyl group went to the less substituted carbon of the triple bond. The reaction of unactivated simple terminal and certain internal acetylenes with benzylindium in THF proceeded smoothly to afford the corresponding benzylation products 18 in good to high yields. The benzyl group was attached to the less substituted unhindered carbon of the triple bond, and indium was attached to the more sterically congested carbon. The reaction of activated nitriles 3 with allylindiums in THF at 70°C gave the corresponding allylationenamination products 4 in high to excellent yields. This reaction provides a useful method for the synthesis of highly functionalized enamines, which are not easily available via conventional methods. The mechanisms on the above three indation reactions are discussed.