title: Photocatalyst size controls electron and energy transfer: selectableE/Zisomer synthesisviaC-F alkenylation.
abstract: Photocatalytic alkene synthesis can involve electron and energy transfer processes. The structure of the photocatalyst can be used to control the rate of the energy transfer, providing a mechanistic handle over the two processes. Jointly considering catalyst volume and emissive energy provides a highly sensitive strategy for predicting which mechanistic pathway will dominate. This model was developeden routeto a photocatalytic Caryl-F alkenylation reaction of alkynes and highly-fluorinated arenes as partners. By judicious choice of photocatalyst, access toE- orZ-olefins was accomplished, even in the case of synthetically challenging trisubstituted alkenes. The generality and transferability of this model was tested by evaluating established photocatalytic reactions, resulting in shortened reaction times and access to complimentaryZ-cinnamylamines in the photocatalytic [2 + 2] and C-H vinylation of amines, respectively. These results show that taking into account the size of the photocatalyst provides predictive ability and control in photochemical quenching events.
authors.affiliation: Department of Chemistry , Oklahoma State University , Stillwater , OK 74078 , USA . Email: jimmie.weaver@okstate.edu.
authors.forename: A
authors.initials: A
authors.lastname: Singh
authors.affiliation: Department of Chemistry , Oklahoma State University , Stillwater , OK 74078 , USA . Email: jimmie.weaver@okstate.edu.
authors.forename: C J
authors.initials: CJ
authors.lastname: Fennell
authors.affiliation: Department of Chemistry , Oklahoma State University , Stillwater , OK 74078 , USA . Email: jimmie.weaver@okstate.edu.
authors.forename: J D
authors.initials: JD
authors.lastname: Weaver