ppm Pd-catalyzed, Cu-free Sonogashira couplings in water using commercially available catalyst precursors.

A new catalyst that derives from commercially available precursors for copper-free, Pd-catalyzed Sonogashira reactions at the sustainable ppm level of precious metal palladium under mild aqueous micellar conditions has been developed. Both the palladium pre-catalyst and ligand are commercially available, bench stable, and highly cost-effective. The catalyst is applicable to both aryl- and heteroaryl-bromides as educts. A wide range of functional groups are tolerated and the aqueous reaction medium can be recycled. An application to a key intermediate associated with an active pharmaceutical ingredient (ponatinib) is discussed

A new, substituted palladacycle for ppm level Pd-catalyzed Suzuki-Miyaura cross couplings in water.

A newly engineered palladacycle that contains substituents on the biphenyl rings along with the ligand HandaPhos is especially well-matched to an aqueous micellar medium, enabling valued Suzuki-Miyaura couplings to be run not only in water under mild conditions, but at 300 ppm of Pd catalyst. This general methodology has been applied to several targets in the pharmaceutical area. Multiple recyclings of the aqueous reaction mixture involving both the same as well as different coupling partners is demonstrated. Low temperature microscopy (cryo-TEM) indicates the nature and size of the particles acting as nanoreactors. Importantly, given the low loadings of Pd invested per reaction, ICP-MS analyses of residual palladium in the products shows levels to be expected that are well within FDA allowable limits

Organometallics in synthesis

xii, 555 p.; 25 c

Status check: biocatalysis; it's use with and without chemocatalysis. How does the fine chemicals industry view this area?

Gallou F, Gröger H, Lipshutz BH. Status check: biocatalysis; it's use with and without chemocatalysis. How does the fine chemicals industry view this area? Green Chemistry . 2023.Biocatalytic processes used alone, as well as part of chemoenzymatic catalysis, would appear to be very attractive areas to several types of companies that make up the fine chemicals industry. These offer, in particular, many opportunities for advances based on enzymatic processes that tend to be highly selective, if not specific, in their applications carried out in environmentally respectful aqueous media. The same is true for chemocatalysis, where many of the most important processes can today be merged with biocatalysis and used together in a single pot, all in water. But notwithstanding these virtues, industrial usage, in fact, is highly variable, at least as of today. This Perspective Article provides the raw, unfiltered yet confidential responses to a series of questions from those at several companies in the fine chemicals industry regarding these topics