Homo-Mannich Reaction of Cyclopropanols: A Versatile Tool for Natural Product Synthesis

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to imine or iminium ion, is one most widely used synthetic methods for synthesis β-amino carbonyl compounds. Nevertheless, homo-Mannich which utilizes a homoenolate as partner and provides straightforward access valuable γ-amino compounds, remains underexplored. This can be largely attributed difficulties in generation manipulation species, despite various equivalents that have been developed. Among developed, cyclopropanol stands out due its intriguing reactivities endowed by highly strained cyclopropane. Upon activation metal, cyclopropyl alcohol prone undergo endocyclic C(sp3)–C(sp3) bond cleavage give β-keto radical intermediate, sets stage diverse range transformations. account outlines our recent progress development reaction applications natural product total synthesis. new methodology classified into two subtypes: 1) with imines ions 2) homo-Mannich-type heteroarenes. Through different ways generate ions, tandem sequential reactions C–H oxidation/homo-Mannich, Bischler–Napieralski/homo-Mannich, asymmetric allylation/homo-Mannich leading rapid assembly core scaffolds sarpagine, koumine, ibophyllidine, Aspidosperma, Melodinus, Kopsia alkaloids. Besides ring-opening indole pyrrole rings deliver schizozygane indolizidine Based on these advancements, we accomplished 29 alkaloids belonging 8 families. In this Account, present complete picture works concerning design, method development, It anticipated methodologies will find broad realm

Language: Английский

Enhancement of toughness and ductility to 1,2,3-triazole Click-cured elastomers via regulation of molecular network and microphase separation

European Polymer Journal, Journal Year: 2025, Volume and Issue: unknown, P. 113835 - 113835

Published: Feb. 1, 2025

Language: Английский