Chemoselectivity in Gold(I)-Catalyzed Propargyl Ester Reactions: Insights From DFT Calculations

Nickel-catalyzed substitution reactions of propargyl halides with organotitanium reagents.

A simple and mild catalytic coupling reaction of propargyl halides with organotitanium reagents is reported. The reaction of propargyl bromide with organo-titanium reagents mediated by NiCl2 (2 mol%) and PCy3 (4 mol%) in CH2Cl2 afforded coupling product allenes in good to excellent yields (up to 95%) at room temperature. However, NiCl2(PPh3)2 was the best catalyst for substituted propargyl hali...

Chemoselectivity in Transfer-Hydrogenation Reactions

Antibody-catalyzed reversal of chemoselectivity.

A monoclonal antibody, 14D9, which has been elicited against a cationic hapten, N-alkyl-N-methyl-3-glutarylamidomethyl piperidinium, in which alkyl = [4-(2-hydroxyethylamido)carbonyl]phenylmethyl, is capable of inverting the intrinsic order of reactivity in a series of structurally related enol ethers and ketals towards hydrolysis. The order of reactivity of compounds 2 (1-methoxy-2-alkylcyclop...

Copper-Catalyzed Decarboxylative Trifluoromethylation of Propargyl Bromodifluoroacetates.

The development of efficient methods for accessing fluorinated functional groups is desirable. Herein, we report a two-step method that utilizes catalytic Cu for the decarboxylative trifluoromethylation of propargyl bromodifluoroacetates. This protocol affords a mixture of propargyl trifluoromethanes and trifluoromethyl allenes.

Mechanism investigation of ketone hydrogenation catalyzed by ruthenium bifunctional catalysts: insights from a DFT study.

In this paper, the mechanism of ketone hydrogenation catalyzed by five Ru bifunctional catalysts with different structural frameworks was studied in detail using density functional theory (DFT). This mechanism contains hydrogen transfer, dehydrogenation of alcohol, and dihydrogen activation fundamental reactions. The involvement of alcohol is also discussed and found with different activities i...