Palladium-catalyzed alkynylation.

Acetylenkupplungen: eine leistungsfähige Methode für den Aufbau von Molekülen

Synthesis of Alkynyl Sulfides by Copper-Catalyzed Thiolation of Terminal Alkynes Using Thiosulfonates.

Turning unreactive copper acetylides into remarkably powerful and mild alkyne transfer reagents by oxidative umpolung

Preparation of a cis-isoprostane synthon.

It was shown that in reactions of aryl iodides with terminal acetylenes catalyzed by palladium complexes, potash or alkali can be used as a base in the interfacial system.

Reactions of terminal acetylenes with aryl iodides catalyzed by palladium complexes under interfacial conditions

1.

The optimum conditions for conducting coupling reactions of terminal acetylenes with organic halides in the presence of amines, CuI, and palladium complexes were determined.




2.

Pd(0)-Pd(PPh3)2 and Pd (II)-R'PdX (PPh3)2 complexes are intermediates in the catalytic reactions of RC≡CH with R'X(“Pd,” Et3N, CuI).

Cross-coupling of terminal acetylenes with organic halides in the R3N-CuI-Pd system

1.

Terminal acetylenes have been reacted with allyl halides under mild conditions to give quantitative yields of the coupling products.




2.

The best base for these reactions is K2CO3 and the most active catalyst is CuI. 3. Under these conditions, the reaction is not accompanied by allyl rearrangement of 1,1-disubstituted prop-1-ene 3-halides.

Synthesis of allylacetylenes from terminal acetylenes and allyl halides

The effect of the nature of the metal M and the organic group R on the reaction of organometallic compounds RM (R = Ph, PhC triple bond C, C/sub 3/H/sub 7/, Allyl; M = Li, Mg, Zn, Cd, Cu Al), produced in situ from Grignard reagents or organolithium compounds and the respective salts, with p-iodoanisole in the presence of palladium complexes PdCl/sub 2/L/sub 2/ (L = PPh/sub 3/, MeCN, dppf) was studied. The organozinc and organoaluminum compounds react with a high degree of selectivity. In the reactions of C/sub 3/H/sub 7/M with p-MeOC/sub 6/H/sub 4/I the highest yield from cross-coupling is obtained with catalysis by the PdCl/sub 2/ (dppf) complex. The mechanism of the formation of the homocoupling products is discussed.

Reactions of organometallic compounds catalyzed by transition metal complexes. XIII. Comparison of the reactivity of organometallic compounds in aryldemetallation reactions catalyzed by palladium complexes

A. B. Ponomarev

Papers

Reactions of terminal acetylenes with aryl iodides catalyzed by palladium complexes under interfacial conditions

Cross-coupling of terminal acetylenes with organic halides in the R3N-CuI-Pd system

Synthesis of allylacetylenes from terminal acetylenes and allyl halides

Reactions of organometallic compounds catalyzed by transition metal complexes. XIII. Comparison of the reactivity of organometallic compounds in aryldemetallation reactions catalyzed by palladium complexes