1228032-75-4Relevant academic research and scientific papers
Palladium-catalyzed oxidative arylhalogenation of alkenes: Synthetic scope and mechanistic insights
Kalyani, Dipannita,Satterfield, Andrew D.,Sanford, Melanie S.
supporting information; experimental part, p. 8419 - 8427 (2010/08/04)
This article describes the development of a Pd-catalyzed reaction for the arylhalogenation (halogen = Cl or Br) of diverse α-olefins by oxidatively intercepting Mizoroki-Heck intermediates. These transformations afford synthetically useful 1,2- and 1,1-arylhalogenated products in good yields with good to excellent selectivities that can be modulated by changing the nature of the halogenating reagent and/or the reaction conditions. The selectivity of these reactions can be rationally tuned by (i) controlling the relative rates of oxidative functionalization versus β-hydride elimination from equilibrating PdII-alkyl species and (ii) stabilization of organometallic PdII intermediates through the formation of π-benzyl adducts. These arylhalogenations exhibit modest to excellent levels of stereoselectivity, and the key carbon-halogen bond-forming step proceeds with predominant retention of stereochemistry at carbon.
