149274-06-6Relevant academic research and scientific papers
Vinylation of aromatic halides using inexpensive organosilicon reagents. Illustration of design of experiment protocols
Denmark, Scott E.,Butler, Christopher R.
, p. 3690 - 3704 (2008)
The preparation of styrenes by palladium-catalyzed cross-coupling of aromatic iodides and bromides with divinyltetramethyldisiloxane (DVDS) in the presence of inexpensive silanolate activators has been developed. To facilitate the discovery of optimal reaction conditions, Design of Experiment (DoE) protocols were used. By the guided selection of reagents, stoichiometries, temperatures, and solvents, the vinylation reaction was rapidly optimized with three stages consisting of ca. 175 experiments (of a possible 1440 combinations). A variety of aromatic iodides undergo cross-coupling at room temperature in the presence of potassium trimethylsilanoate using Pd(dba) 2 in DMF in good yields. Triphenylphosphine oxide is needed to extend catalyst lifetime. Application of these conditions to aryl bromides was accomplished by the development of two complementary protocols. First, the direct implementation of the successful reaction conditions using aryl iodides at elevated temperature in THF provided the corresponding styrenes in good to excellent yields. Alternatively, the use of potassium triethylsilanolate and a bulky "Buchwald-type" ligand allows for the vinylation reactions to occur at or just above room temperature. A wide range of bromides underwent coupling in good yields for each of the protocols described.
Functionalization of Alkenyl C-H Bonds with D 2 O via Pd(0)/Carboxylic Acid Catalysis
Bigi, Franca,Camedda, Nicola,Cera, Gianpiero,Maestri, Giovanni,Maggi, Raimondo,Serafino, Andrea
supporting information, p. 1762 - 1772 (2020/06/08)
We report herein a simple catalytic method for the extensive labeling of alkenyl C-H bonds through the combination of a palladium(0) complex and a carboxylic acid in the presence of deuterium oxide. The reaction can be applied to a variety of terminal alkenes and the best results are obtained with aryl-substituted examples. This method represents a convenient approach for the preparation of extensively labeled chemicals from the cheapest and safest source of deuterium.
