C–H Halogenation of Pyridyl Sulfides Avoiding the Sulfur Oxidation: A Direct Catalytic Access to Sulfanyl Polyhalides and Polyaromatics - Université de Bourgogne Accéder directement au contenu
Article Dans Une Revue ACS Omega Année : 2019

C–H Halogenation of Pyridyl Sulfides Avoiding the Sulfur Oxidation: A Direct Catalytic Access to Sulfanyl Polyhalides and Polyaromatics

Résumé

Palladium-catalyzed oxidative C−H halogenation and acetoxylation reactions of S-unprotected sulfides, selectively directed by pyridinyl groups, allows the formation of C−X bonds (X = I, Br, Cl, OAc) by using simple halosuccinimide or phenyliodine diacetate (PIDA) oxidants. The undesired formation of sulfoxides and/or sulfones, which are usually observed under oxidative conditions, is fully obviated. Under the solvent-dependent conditions that we proposed, sulfide C−H functionalization is achieved in less than 1 h without any direct electrophilic halogenation at the pyridine moiety. NDirected ortho-C−H activation of aryl also facilitates dibromination reactions which are hardly accessible with sulfone and sulfoxide counterparts because of their higher structural rigidity. This general method gives a straightforward access to polyhalide sulfides, without an organosulfur reduction step or protection−deprotection sequence. Polyhalide sulfides are valuable synthons that give a practical entry to new constrained polyaromatic and biphenyl sulfides, including synthetically challenging unsymmetrical examples.

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Catalyse

Dates et versions

hal-03664143 , version 1 (10-05-2022)

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Johan Guilbaud, Awatef Selmi, Majed Kammoun, Sylvie Contal, Christian Montalbetti, et al.. C–H Halogenation of Pyridyl Sulfides Avoiding the Sulfur Oxidation: A Direct Catalytic Access to Sulfanyl Polyhalides and Polyaromatics. ACS Omega, 2019, 4 (24), pp.20459-20469. ⟨10.1021/acsomega.9b01636⟩. ⟨hal-03664143⟩
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