72693-12-0Relevant articles and documents
Terminal-Selective Functionalization of Alkyl Chains by Regioconvergent Cross-Coupling
Dupuy, Stéphanie,Zhang, Ke-Feng,Goutierre, Anne-Sophie,Baudoin, Olivier
supporting information, p. 14793 - 14797 (2016/11/23)
Hydrocarbons are still the most important precursors of functionalized organic molecules, which has stirred interest in the discovery of new C?H bond functionalization methods. We describe herein a new step-economical approach that enables C?C bonds to be constructed at the terminal position of linear alkanes. First, we show that secondary alkyl bromides can undergo in situ conversion into alkyl zinc bromides and regioconvergent Negishi coupling with aryl or alkenyl triflates. The use of a suitable phosphine ligand favoring Pd migration enabled the selective formation of the linear cross-coupling product. Subsequently, mixtures of secondary alkyl bromides were prepared from linear alkanes by standard bromination, and regioconvergent cross-coupling then provided access to the corresponding linear arylation product in only two steps.
Functionalization of non-activated C-H bonds in ketones and imines with HF/SbF5/CCl4
Thibaudeau, Sébastien,Martin-Mingot, Agnès,Jouannetaud, Marie-Paule,Jacquesy
, p. 6643 - 6649 (2007/10/03)
Reaction of cyclic ketones 2-6 and imines 15-17 in HF/SbF5 in presence of CCl4 yield hydroxy or fluoroderivatives, hydride abstraction occurring at a site located far from the functional group. Whereas ketones 2-5 yield only hydroxy derivatives, through cyclic carboxonium ion, imines 15, 16 N-protonated in the media conditions give only fluoroderivatives 18, 19, respectively, after quenching with HF-pyridine. Ring contraction is operative when starting from large membered ring ketones 24 and 25, and imine 26, leading to a mixture of hydroxy or fluoro cyclohexanones and/or cycloheptanones.
