Room-Temperature Suzuki−Miyaura Couplings in Water Facilitated by Nonionic Amphiphiles

Abstract

Use of a dilute aqueous solution containing a nonionic amphiphile allows efficient Suzuki-Miyaura cross-couplings of arylboronic acids with a wide array of aryl halides and pseudohalides, including sterically hindered and lipophilic substrates, in most cases at room temperature.

Suzuki cross-coupling in aqueous media

“…However, tetra-coordinated organoborates have gained increased popularity due to their ready availability and ease of handling. 5,[38][39][40][41][42] Especially organotrifluoroborates offer substantial benefits. They are air and moisture stable and can be easily prepared and purified; 5,43 however their use as substrates in Suzuki reactions is only marginally exploited.…”

Ring‐Closing Metathesis at Room Temperature within Nanometer Micelles using Water as the Only Solvent

“…Use of prenylated amine 4 is particularly noteworthy, and is suggestive that such terminally disubstituted olefins can also be used in (previously unprecedented) RCM reactions. Reaction work-up and product isolation free of any PTS is very straightforward, a general observation as noted in A C H T U N G T R E N N U N G earlier uses of this amphiphile [9][10][11] (also, see procedure below).…”

“…[8] Their conclusion was that such reactions may not require any surfactant; that water alone could in many cases afford cyclized products in high yields. Recently, the 3-component amphiphile PTS (1, (polyoxyethanyl a-tocopheryl sebacate) has been introduced as a "general purpose" nonionic amphiphile, allowing for Heck, [9] Suzuki, [10] and olefin cross-metathesis (CM) reactions [11] to occur with lipophilic substrates also in pure water at room temperature. Unsymmetrical CM reactions were shown to proceed far better under the influence of PTS than on water, [4,5,8] reactions presumably taking place within the ca.…”

Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

“…The biaryl motif can be found in numerous natural products, agrochemicals, drugs, polymers, ligands and thus triggered the attention of the scientific community for a wide range of applications [2][3][4][5][6][7][8][9]. If the formation of a biphenyl motif belongs nowadays to a textbook knowledge, the past decade has witnessed spectacular innovations and improvements such as ligandless transformations [10], supported or nanostructured catalytic systems [11][12][13], performing additives [14,15], neat and/or aqueous conditions [2,13,15], MW activations [10] for example.…”

“…Although the presence of a ligand is not strictly mandatory, increase of selectivity, the use of poorly reactive chlorides, room temperature conditions remains challenging and usually requires a ligand [11,13,15,16]. Additionally, preformed and geometrically constrained catalytic systems appears as crucial features beneficial to a catalytic activity enhancement [8,17].…”