80155-86-8

Upstream product

• 928-49-4 hex-3-yne 
• 65-85-0 benzoic acid 

Downstream Products

• 1384266-66-3 (R)-hexan-3-yl benzoate 

Relevant academic research and scientific papers

Gold(i)-catalyzed addition of carboxylic acids to internal alkynes in aqueous medium

We report herein the efficient hydro-oxycarbonylation of symmetrical and unsymmetrical internal alkynes with carboxylic acids in water at 60 °C, employing the catalytic system [AuCl(PPh3)]/AgOAc (5 mol%). This simple and eco-friendly protocol allows for the synthesis of a wide variety of trisubstituted enol esters (37 examples) in high yields and with complete Z-stereoselectivity. The use of microwave irradiation as an alternative energy source has also been evaluated.

Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters

The catalytic asymmetric hydrogenation of trisubstituted enol esters using Rh catalysts bearing chiral phosphine-phosphite ligands (P-OP) has been studied. Substrates covered comprise α,β-dialkyl, α-alkyl-β-aryl, and α,β-diarylvinyl esters, the corresponding hydrogenation products being suitable precursors to prepare synthetically relevant chiral nonfunctionalized alcohols. A comparison of reactivity indicates that it decreases in the order: α,β-dialkyl > α-alkyl-β-aryl > α,β-diaryl. Based on the highly modular structure of P-OP ligands employed, catalyst screening identified highly enantioselective catalysts for α,β-dialkyl (95-99% ee) and nearly all of α-alkyl-β-aryl substrates (92-98% ee), with the exception of α-cyclohexyl-β-phenylvinyl acetate which exhibited a low enantioselectivity (47% ee). Finally, α,β-diarylvinyl substrates showed somewhat lower enantioselectivities (79-92% ee). In addition, some of the catalysts provided a high enantioselectivity in the hydrogenation of E/Z mixtures (ca. Z/E = 75:25) of α,β-dialkylvinyl substrates, while a dramatic decrease on enantioselectivity was observed in the case of α-methyl-β-anisylvinyl acetate (Z/E = 58:42). Complementary deuteration reactions are in accord with a highly enantioselective hydrogenation for both olefin isomers in the case of α,β-dialkylvinyl esters. In contrast, deuteration shows a complex behavior for α-methyl-β-anisylvinyl acetate derived from the participation of the E isomer in the reaction.

Ruthenium-Catalyzed Hydrocarboxylation of Internal Alkynes

The application of the highly efficient ruthenium catalyst [Ru(CO)2{P(p-CF3-C6H4)3}2(O2CPh)2] (1) in the selective syn-addition of carboxylic acids to internal alkynes

Hydrocarboxylation of unactivated internal alkynes with carboxylic acids catalyzed by dinuclear palladium complexes

Dinuclear palladium complexes catalyzed addition reactions of carboxylic acid O-H bond to unactivated internal alkynes. The reaction afforded a trans-adduct selectively.

Gold(I)-catalyzed addition of carboxylic acids to alkynes

Au(I)-catalyzed hydroacyloxylation of alkynes with carboxylic acids is described. PPh3AuCl/AgPF6 catalyst affords the Markonikov addition products, whereas PPh3AuCl/AgOTf catalyst gives the more stable isomerized products