Abstract: The synthesis of natural products containing eight-membered heterocycles has proved to be highly challenging. In this contribution, an environmentally benign synthesis of benzo-1,5 dioxocines via ynamides is reported. A new class of ynamides was prepared by using a green and mild synthetic pathway. The eight-membered heterocycles fused to aryl groups were obtained from propargylic...[more]
Abstract: We report the first examples of metal-promoted double geminal activation of C(sp 3 )–H bonds of the N–CH 2 –N moiety in an imidazole-type heterocycle, leading to nickel and palladium NHC complexes under mild conditions. Reaction of the new electron-rich diphosphine 1,3-bis((di- tert -butylphosphaneyl)methyl)-2,3-dihydro-1 H -benzo[ d ]imidazole ( 1 ) with [PdCl 2 (cod)] occurred...[more]
Abstract: A combined experimental/theoretical study of Ni pincer complexes with a bridgehead pyrimidine-based NHC and arylphosphino side arms revealed unique features about stepwise C–H activation, ethylene insertion into the Ni–H bond of an isolated complex followed by ethyl migration with C–CNHC coupling, and an unprecedented C–P bond activation affording via PPh2 migration a NiII complex...[more]
Abstract: Citronellol, one of the most used fragrance compounds worldwide, is one ingredient of Fragrance Mix II used to assess skin allergy to fragrances in dermatitis patients. Pure citronellol is non-allergenic. Main issue is it autoxidizes when exposed to air becoming then allergenic. The increased skin sensitizing potency of air-exposed citronellol has been attributed to the hydroperoxides...[more]
Abstract: IspG (also called GcpE) is an oxygen-sensitive [4Fe-4S] enzyme catalyzing the penultimate step of the methylerythritol phosphate (MEP) pathway, a validated target for drug development. It converts 2-C-methyl-d-erythritol-2,4-cyclo-diphosphate (MEcPP) into (E)-4-hydroxy-3-methyl-but-2-enyl-1-diphosphate (HMBPP). The reaction, assimilated to a reductive dehydration, involves redox...[more]
Abstract: The non-mevalonate or also called MEP pathway is an essential route for the biosynthesis of isoprenoid precursors in most bacteria and in microorganisms belonging to the Apicomplexa phylum, such as the parasite responsible for malaria. The absence of this pathway in mammalians makes it an interesting target for the discovery of novel anti-infectives. As last enzyme of this pathway,...[more]
Abstract: The first synthesis of gem-difluorinated ene–ynamides is presented via deprotonation of trifluoromethylated N-allenamides and δ extrusion of fluorine. These highly reactive building blocks, owing to their dual functional groups, offer a unique entry to difluorinated dienes and to stereodefined, monofluoro-substituted dienes. Stereoselective addition to the ynamide moiety led to...[more]