Suzuki–Miyaura Micellar Cross-Coupling in Water, at Room Temperature, and under Aerobic Atmosphere

Abstract

Recently, oxygen-equilibrated water solutions of Kolliphor EL, a well-known surfactant, have been seen to form nanomicelles with oxygen-free cores. This has prompted the successful testing of the core environment as a green medium for palladium-catalyzed Suzuki-Miyaura cross couplings. The versatility of these conditions is endorsed by several examples, including the synthesis of relevant molecular semiconductors. The reaction medium can also be recycled, opening the way for an extremely easy and green chemistry compliant methodology.

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

“…Interesting observations have been noted in some cases of surfactants bearing charge(s), such as greatly enhanced reaction rates between polar substrates, where, in the presence of cationic or anionic surfactants, the normal exchange process between micellar arrays through water by an educt may be slowed due to electrostatic attractions, keeping them in closer proximity to the micelles in which their reactions take place . Another interesting observation that was not scripted includes the lack of solubility of dissolved oxygen within a particular surfactant‐derived nanomicelle, that has perhaps clear implications for the lifetime of an oxygen‐sensitive phosphine ligand‐chelated metal catalyst . On the other hand, a surfactant has been specifically designed to increase molecular oxygen solvation within the core of the micelles for oxidation reactions .…”

“…While the poor solubility of molecular O 2 in the core of the micelle is an asset for sensitive phosphine‐based ligands, it can be problematic with oxidation reactions that require oxygen gas. To address that limitation, Rodionov and co‐workers introduced an enzyme‐inspired surfactant enabling chemoselective oxidation of benzylic, allylic and heteroaromatic alcohols to their corresponding aldehydes in the presence of CuSO 4 in water (Scheme ) .…”

“…[34,64,65,69,82] Another interesting observation that wasn ot scriptedi ncludes the lack of solubility of dissolved oxygen within ap articular surfactant-derived nanomicelle, that has perhaps clear implicationsf or the lifetime of an oxygen-sensitive phosphine ligand-chelated metal catalyst. [24] On the other hand, as urfactant hasb een specifically designed to increase molecular oxygen solvation within the core of the micelles for oxidation reactions. [67] These and several other fascinating and intriguing discoveries, as detailsa ssociated with the various topics in this review,a re presented herein.…”

Effective BI‐DIME Ligand for Suzuki–Miyaura Cross‐Coupling Reactions in Water with 500 ppm Palladium Loading and Triton X

“…Over the past two decades, several research groups have made significant contributions to the field of palladium‐catalyzed SMC reactions by using water as the main reaction medium . However, most water‐based procedures for homogenous SMC reactions suffer from high catalyst loading,,,,,, the need for an organic co‐solvent,, or narrow substrate scope ,,,,,…”

Syntheses of Organic Semiconductors in Water. Recent Advancement in the Surfactants Enhanced Green Access to Polyconjugated Molecules

“…Data taken from ref. [46] Entry Scheme 2 derivatives hardly qualify as organic semiconductors, in fact none of them possesses a particularly extended πconjugated structure. One relevant and almost ubiquitous characteristic observed at increased conjugation length is poor solubility.…”