115584-90-2

Upstream product

• 536-74-3 phenylacetylene 
• 870-63-3 prenyl bromide 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 3757-88-8 tributylstannylethynylbenzene 
• 932-88-7 1-iodo-2-phenylethyne 

Relevant academic research and scientific papers

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.

Copper catalyzed regioselective coupling of allylic halides and alkynes promoted by weak inorganic bases

Allylic halides and terminal alkynes couple under CuI catalysis in DMSO or DMF solution. In most cases, sodium carbonate or bicarbonate is sufficient to promote the reaction; less reactive alkynes require catalytic amounts of DBU. Bifunctional alkynes and halides can be reacted selectively according to the stoichiometry used. Trimethylsilyl, hydroxyl, ester and halide groups are tolerated in the alkyne. Most halides react without allylic rearrangement. The method is suitable for the synthesis of functionalized enynes.

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.

Regioselectivity in coupling of allyl halides with copper acetylene complexes

A regiselectivity of 1,4-enynes formation in reaction of σ-acetylene copper complexes (copper acetylenides, alkynyliodocuprates, dialkynylcuprates) with various allyl halides was investigated. The most selective reaction was observed between dialkynylcuprates and geranyl bromide.

Nickel-Catalyzed Cross-Coupling Reaction of Allyl Halides with Alkynyltins

A cross-coupling reaction of allyl halides 1 with alkynyltins 3 in the presence of "Ni(PR3)n" (R = Ph, OEt, or OPh) catalyst was carried out in THF at reflux to give 1,4-enynes.The regioselectivity of the coupling of 1f-i with 3a was investigated in the presence of various phosphorus ligands.Interestingly, prenyl (1j) and geranyl chlorides (1k) selectively reacted with 3 at the more-hindered positions of substituted η3-allylnickel intermediates 21 (M = Ni) to yield 23 and 25, respectively.Regioselectivity in these reactions may result from greater steric crowding between the phosphorus ligand and the disubstituted position in 26b than in 26a.In contrast, the palladium-catalyzed reactions of 1j and 1k with 3 selectively gave 22 and 24, respectively.Thus, the steric crowding in a Pd analogue of 26b is less than that in a Ni analogue of 26b, since Pd has a larger covalent radius than Ni.

COPPER(I) AND PHASE TRANSFER CATALYSED ALLYLIC SUBSTITUTION BY TERMINAL ALKYNES

The Cu(I) catalysed allylic substitution of (un)substituted allyl halides by alk-1-ynes can proceed smoothly at or near room temperature under solid-liquid phase transfer conditions.