Radical “On Water” Addition to the C═N Bond of Hydrazones: A Synthesis of Isoindolinone Derivatives

Abstract

A radical "on water" addition to the C═N bond of hydrazones has been described. Hydrazone, diphenylsilane, alkyl iodide, and triethylborane afforded the corresponding addition products "on water" in good yields. A significant solvent effect was observed from the water. The developed protocol can be applied to the synthesis of 3-substituted isoindolinone derivatives. Moreover, the process offers environmentally benign tin-free radical reaction conditions.

Modular Synthesis of Alkylarylazo Compounds via Iron(III)-Catalyzed Olefin Hydroamination

“…On the other hand, radical addition reactions serve as an efficient and practical strategy for the construction of new C–C, C–O, and C–N bonds . However, the scope of intermolecular radical acceptors is still limited to the most commonly used C–C double or triple bonds, many C–N double bonds, and few C–O double bonds (Figure b). Therefore, exploration of a broader acceptor pool in radical chemistry remains an ongoing challenge.…”

Recent Advances and Prospects of Organic Reactions “On Water”

“…On water addition to the C=N bond of hydrazones by radical reaction with alkyl iodide as radical precursors using diphenylsilane and triethylborane was reported (Scheme ) . Et 3 B in the presence of oxygen generates an ethyl radical that reacts with the alkyl halide to give alkyl radical.…”

Chemistry Takes a Bath: Reactions in Aqueous Media

“…In this special issue of The Journal of Organic Chemistry, there are 30 articles describing research that reflects a variety of modern advancements, all realized in aqueous media. Synthesis is the aim of most of the papers, which include sustainable methodology, 18−20 asymmetric catalysis, 21 "on-water" chemistry, 22,23 micelle-enabled reactions, 24−29 heterogeneous catalysis, 30−33 electro- 34 and photochemistry, 28,35 and reactions mediated by enzymes. 36−41 These reports also highlight how aqueous reactions facilitate the synthesis and modification of highly hydrophilic compounds, such as amino acids, 40 peptides, 42 and carbohydrates.…”

“…In this special issue of The Journal of Organic Chemistry , there are 30 articles describing research that reflects a variety of modern advancements, all realized in aqueous media. Synthesis is the aim of most of the papers, which include sustainable methodology, − asymmetric catalysis, “on-water” chemistry, , micelle-enabled reactions, − heterogeneous catalysis, − electro- and photochemistry, , and reactions mediated by enzymes. − These reports also highlight how aqueous reactions facilitate the synthesis and modification of highly hydrophilic compounds, such as amino acids, peptides, and carbohydrates . But in addition to synthesis, we also find papers focused on biology, including bio-orthogonal reactions − and characterization of therapeutic compounds, thus attesting to the diversity of topics in this compendium dedicated to “Chemistry in Water”, as illustrated on the cover of this thematic issue.…”