14255-25-5

Upstream product

• 673-32-5 1-Phenylprop-1-yne 
• 762-72-1 allyl-trimethyl-silane 
• 6084-17-9 2-chloro-1-phenylpropan-1-one 
• 106-95-6 allyl bromide 
• 2114-00-3 2-bromo-1-phenyl-1-propanone 
• 74-85-1 ethene 
• 157397-76-7 (E)-methyl 3-phenylbut-2-enyl carbonate 
• 72824-04-5 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 4518-65-4 (1-methoxyprop-1-en-1-yl)benzene 
• 53317-08-1 9-allyl-9-bora-bicyclo[3.3.1]nonane 
• 16277-67-1 3-methoxy-1-phenylpropene 

Relevant academic research and scientific papers

A regioselectivity switch in Pd-catalyzed hydroallylation of alkynes

By exploiting the reactivity of a vinyl-Pd species, we control the regioselectivity in hydroallylation of alkynes under Pd-hydride catalysis. A monophosphine ligand and carboxylic acid combination promotes 1,5-dienes through a pathway involving isomerization of alkynes to allenes. In contrast, a bisphosphine ligand and copper cocatalyst favor 1,4-dienes via a mechanism that involves transmetalation. Our study highlights how to access different isomers by diverting a common organometallic intermediate.

"Design" of boron-based compounds as pro-nucleophiles and co-catalysts for indium(I)-catalyzed allyl transfer to various Csp 3-type electrophiles

We have recently uncovered a general indium(I)-catalyzed method for allylations and propargylation of acetals and ketals with a water- and air-stable allyl boronate. By using a more reactive allyl borane, we have successfully extended this methodology to the more challenging C-C coupling with ethers. Herein, we report an improved methodology for the indium(I)-catalyzed allylation of acetals and ethers, through combination of the allyl boronate with a commercially available "hard" Lewis acid, B-methoxy-9-BBN (BBN=borabicyclo[3.3.1]nonane), as an effective co-catalyst. Significantly, our work highlights for the first time the correlation between the Lewis acidity of "electrophilic" boron-based compounds and their " nucleophilic" reactivity in Csp3-Csp3 couplings, catalyzed by a "soft" low-oxidation main group metal. In addition, we also report several applications of these methodologies to the selective synthesis of various carbohydrate derivatives. Copyright

Nickel-catalyzed allylic substitution of simple alkenes

Nickel-catalyzed intermolecular allylic substitution of simple alkenes (ethylene and alpha olefins) is described. This method is the first catalytic intermolecular process for direct allylation of nonconjugated, nonstrained simple alkenes. Catalyst loadings as low as 2.5 mol % Ni afford the desired product in high yield in both gram-scale and smaller scale coupling reactions.

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.

Aluminum chloride catalyzed stereo- and regiospecific allylsilylation of alkynes: a convenient route to silyldienes

Allyltrimethylsilane reacts with phenylalkynes in the presence of aluminum chloride catalyst under mild conditions to afford silylphenyldienes in moderate yield.In this allylsilylation reaction, the silyl group adds regioselectively to the terminal carbon and the allyl group to the inner carbon of the triple bond.The allylsilylation of phenylacetylene gives the allylsilylated product having the silyl and allyl groups in the cis-position, while diphenylacetylene gives the trans product.The allylic inversion was also observed in the allylsilylation with the stereohomogeneous (Z)-crotyltrimethylsilane.These results are consistent with the initial formation of trimethylsilyl cation intermediate and a stepwise process of allylsilylation.Keywords: Alkylsilylation; Alkynes; Allylic inversion; Allylsilanes; Stereoselectivity; Regioselectivity