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Reducing the use of solvents is an important aim of green chemistry. Using micelles self-assembled from amphiphilic molecules dispersed in water (considered a green solvent) has facilitated reactions of organic compounds. When performing reactions in micelles, the hydrophobic effect can considerably accelerate apparent reaction rates, as well as enhance selectivity. Here, we review micellar reaction media and their potential role in sustainable chemical production. The focus of this review is applications of engineered amphiphilic systems for reactions (surface-active ionic liquids, designer surfactants, and block copolymers) as reaction media. Micelles are a versatile platform for performing a large array of organic chemistries using water as the bulk solvent. Building on this foundation, synthetic sequences combining several reaction steps in one pot have been developed. Telescoping multiple reactions can reduce solvent waste by limiting the volume of solvents, as well as eliminating purification processes. Thus, in particular, we review recent advances in “one-pot” multistep reactions achieved using micellar reaction media with potential applications in medicinal chemistry and agrochemistry. Photocatalyzed reactions in micellar reaction media are also discussed. In addition to the use of micelles, we emphasize the process (steps to isolate the product and reuse the catalyst).
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Aqueous micellar technology: an alternative beyond organic solvents
Solvents are the major source of chemical waste from synthetic chemistry labs. Growing attention to more environmentally friendly sustainable processes demands novel technologies to substitute toxic or hazardous solvents. If not always, sometimes, water can be a suitable substitute for organic solvents, if used appropriately. However, the sole use of water as a solvent remains non-practical due to its incompatibility with organic reagents. Nonetheless, over the past few years, new additives have been disclosed to achieve chemistry in water that also include aqueous micelles as nanoreactors. Although one cannot claim micellar catalysis to be a greener technology for every single transformation, it remains the sustainable or greener alternative for many reactions. Literature precedents support that micellar technology has much more potential than just as a reaction medium, i.e. , the role of the amphiphile as a ligand obviating phosphine ligands in catalysis, the shielding effect of micelles to protect water-sensitive reaction intermediates in catalysis, and the compartmentalization effect. While compiling the powerful impact of micellar catalysis, this article highlights two diverse recent technologies: (i) the design and employment of the surfactant PS-750-M in selective catalysis; (ii) the use of the semisynthetic HPMC polymer to enable ultrafast reactions in water.
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- Award ID(s):
- 2044778
- PAR ID:
- 10397119
- Date Published:
- Journal Name:
- Chemical Communications
- ISSN:
- 1359-7345
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3CC00127J
