- Palladium-Catalyzed Alkene Carboalkoxylation Reactions of Phenols and Alcohols for the Synthesis of Carbocycles
-
Intermolecular alkene difunctionalization reactions between terminal alkenes bearing a pendant aryl or alkenyl triflate electrophile and exogenous alcohol or phenol nucleophiles are described. These transformations afford substituted indanyl or alkylidene
- White, Derick R.,Herman, Madeline I.,Wolfe, John P.
-
p. 4311 - 4314
(2017/08/23)
-
- Developing the Saegusa-Ito Cyclisation for the Synthesis of Difluorinated Cyclohexenones
-
Palladium(II)-catalysed cycloalkenylation (Saegusa-Ito cyclisation) has been used for the first time to transform difluorinated silylenol ethers to difluorinated cycloalkenones under mild conditions. The silylenol ether precursors were prepared in two high-yielding steps from trifluoroethanol, and cyclised in moderate to good yields. A combination of air and copper(I) chloride in acetonitrile gave the turnover of the initial palladium(II) salt, whereas the provision of an oxygen atmosphere ensured more rapid reaction. Annulations required a minimum level of substitution on the chain, but failed when the alkene was substituted. Annelations allowed a range of n,6-bicyclic systems to be prepared and afforded three products, in which heterocycles were fused to the new cyclohexenone. The least substituted system explored underwent cyclisation followed by terminal oxidation to a cyclic enal, which corresponded to a Wacker product of unusual regiochemistry.
- Percy, Jonathan M.,McCarter, Adam W.,Sewell, Alan L.,Sloan, Nikki,Kennedy, Alan R.,Hirst, David J.
-
p. 19119 - 19127
(2016/01/26)
-