Personne : Jayaraman, Arumugam
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Jayaraman
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Arumugam
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Groupe Fontaine, Synthèse Organométallique, Université Laval
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ncf11914446
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Publication Accès libre Metal-free borylative dearomatization of indoles : exploring the divergent reactivity of aminoborane C–H borylation catalysts(Royal Society of Chemistry, 2018-05-07) Fontaine, Frédéric-Georges; Misal Castro, Luis Carlos; Jayaraman, Arumugam; Desrosiers, VincentWhile the dearomatization of indoles by carbon–boron bond forming reactions is new and quite promising, they are so far mainly metal-catalyzed. Here, we establish the use of metal-free catalysts in promoting such reactions in an atom-efficient way. The in situ generated ambiphilic aminoborane catalyst (1-Pip-2-BH2-C6H4)2 (Pip = piperidyl) promotes borylative dearomatization of various 1-arylsulfonyl indoles with pinacolborane in a syn addition fashion, with H and Bpin groups added respectively to the 2 and 3 positions of indoles. Catalysis proceeds with good to excellent conversion and essentially with complete regio- and diastereoselectivity. From mechanistic insights and DFT computations, we realized and established that prototypical boranes can also catalyze this borylative dearomatization.Publication Accès libre Revisiting the reduction of indoles by hydrobranes : a combined experimental and computational study(ScienceDirect, 2019-02-27) Powell-Davies, Henry; Fontaine, Frédéric-Georges; Jayaraman, ArumugamA combined experimental and density functional computational study was used to probe the mechanism for the reduction of indoles using simple borane BH₃·DMS (DMS = dimethyl sulfide). Experimental and computational studies all steer to the formation of the reduced species 1-BH₂-indolines as the resting state for this reaction, as opposed to the historically presumed formation of the unreduced 1-BH₂-indoles, before the addition of a proton source to form the final product indolines. Furthermore, it was observed that molecular H₂ was generated and consumed in the reaction. Computations put forward hydroboration followed by protodeborylation as the very reasonable mechanistic route for the formation of experimentally observed major intermediate 1-BH₂ indolines. For the H₂ consumption in the reaction, computations suggest the frustrated Lewis pair-type heterolytic splitting of H₂ by a bis(3-indolinyl)borane intermediate.