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Relevant academic research and scientific papers

Mitsunobu C-Alkylation of Meldrum's Acids

C-Dialkylation of Meldrum's acid (2a) and 5-benzyl Meldrum's acid (2b) can be achieved through Mitsunobu dehydration using allylic and arylmethyl alcohols as alkylating agents. This is the first time that the Mitsunobu reaction is successfully applied to the C-alkylation of a highly enolizable cyclic β-dicarbonyl system. With primary (allylic and arylmethyl) alcohols, the alkylations always take place at the carbon bearing the hydroxy group. For secondary allylic alcohols, a catalytic amount of Pd(0) must be added to enhance the regioselectivity of C-alkylation over O-alkylation. With (Ph3P)4Pd(0) as a catalyst, the reaction occurs specifically at the less hindered carbon, and the configuration of the resultant double bond is always trans. Attempts to monoalkylate Meldrum's acids 2a and 2b failed.

Green and Scalable Palladium-on-Carbon-Catalyzed Tsuji–Trost Coupling Reaction Using an Efficient and Continuous Flow System

The first continuous flow Tsuji–Trost coupling reaction between allylic compounds and various nucleophiles has been successfully achieved within only around 40 s during a single pass through a cartridge filled with palladium on carbon (Pd/C). Two methods have been designed by using the H-cube ThalesNano technology that enable the efficient production of added-value compounds on the gram scale with high productivity. Under the optimized conditions, the cartridge catalyst can be used for 60 min of continuous processing without a decrease in reactivity. A large range of substrates and nucleophiles have successfully been submitted to the standard methods, giving good-to-excellent yields and productivity.

Et3B-promoted, Pd(0)-catalyzed allylation of active methylene compounds with allylic alcohols

Triethylborane promotes the Pd(0)-catalyzed allylation of active methylene compounds (Meldrum's acid and malonates) with a variety of allylic alcohols. The reaction proceeds smoothly at room temperature and provides the allylation products in good yield. (C) 2000 Elsevier Science Ltd.

Direct palladium/carboxylic acid-catalyzed C-allylation of cyclic 1,3-diones with allylic alcohols in water

The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of cyclic 1,3-diones using allylic alcohols directly gave the corresponding C-allylated products in good yields.

Practical Pd/C-mediated allylic substitution in water

Pd/C-mediated allylic substitution in water is described as an interesting alternative to classical homogeneous conditions. The reaction applied to allylic acetates showed a wide range of compatibility with various nitrogen, sulfur, oxygen, and carbon nucleophiles. Notably, the method features inexpensive reagents and a nontoxic solvent. Moreover, measurement of the palladium content in water by ICP-MS shows low palladium contamination (4 ppm) of the solvent, rendering this method safer for the environment compared to homogeneous conditions. The first asymmetric example of Pd/C-mediated allylic substitution is also disclosed.

Direct allylic substitution of allyl alcohols by carbon pronucleophiles in the presence of a palladium/carboxylic acid catalyst under neat conditions

The reaction of allylic alcohols with carbon pronucleophiles in the presence of the Pd(PPh3)4/carboxylic acid combined catalytic system, under neat conditions (without an organic solvent or without water as the solvent) enabled the direct allylation of the pronucleophiles, giving the corresponding allylated products in high yields.

Triethylborane as an efficient promoter for palladium-catalyzed allylation of active methylene compounds with allyl alcohols

Without prior activation of allyl alcohols, allylation of a variety of active methylene compounds with allyl alcohols proceeds smoothly at rt-50°C in the presence of catalytic amounts of Pd(OAc)2 (1-10mol%), Et 3B (30-240mol%), a phosphine ligand (1-20mol%), and a base (0 to 50-60mol%).

Palladium-catalyzed, carboxylic acid-assisted allylic substitution of carbon nucleophiles with allyl alcohols as allylating agents in water

(Matrix presented) Allylic substitution of allyl alcohols in water as a suspension medium has been realized using a combination of tetrakis(triphenylphosphine)-palladium and a carboxylic acid such as 1-adamantanecarboxylic acid. Various substrates turned out to be applicable to this catalytic system.

PALLADIUM CATALYZED C-ALLYLATION OF HIGHLY ACIDIC CARBO AND HETEROCYCLIC β-DICARBONYL COMPOUNDS

Highly acidic carbo and heterocyclic β-dicarbonyl compounds such as barbituric acid, 3,5-dimethyl-2H-1,2,6-thiadiazine 1,1-dioxide, cyclohexane-1,3-dione, tetronic acids, Meldrum acid and 1,2-diphenylpyrazolidine-3,5-dione are efficiently C-allylated with primary and secondary allylating agents under palladium catalysis.