10.1021/jacs.7b10009.s002 Guang-Zu Wang Guang-Zu Wang Rui Shang Rui Shang Wan-Min Cheng Wan-Min Cheng Yao Fu Yao Fu Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature American Chemical Society 2017 ground-state reactivity alkyl halides palladium-catalyzed cross-coupling reactions 50 years oxidative addition application undesired β- hydride elimination eliminable β- hydrogen atoms palladium complexes light-emitting diodes Unactivated Alkyl Halides room temperature phosphine ligand system alkyl bromides palladium-catalyzed Heck reaction proceeds Room Temperature photoexcited-state reactivity Irradiation-Induced Heck Reaction ligand system alkyl electrophiles Nobel-Prize-winning transformation 2017-11-08 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Irradiation-Induced_Heck_Reaction_of_Unactivated_Alkyl_Halides_at_Room_Temperature/5616502 The palladium-catalyzed Mizoroki–Heck reaction is arguably one of the most significant carbon–carbon bond-construction reactions to be discovered in the last 50 years, with a tremendous number of applications in the production of chemicals. This Nobel-Prize-winning transformation has yet to overcome the obstacle of its general application in a range of alkyl electrophiles, especially tertiary alkyl halides that possess eliminable β-hydrogen atoms. Whereas most palladium-catalyzed cross-coupling reactions utilize the ground-state reactivity of palladium complexes under thermal conditions and generally apply a single ligand system, we report that the palladium-catalyzed Heck reaction proceeds smoothly at room temperature with a variety of tertiary, secondary, and primary alkyl bromides upon irradiation with blue light-emitting diodes in the presence of a dual phosphine ligand system. We rationalize that this unprecedented transformation is achieved by utilizing the photoexcited-state reactivity of the palladium complex to enhance oxidative addition and suppress undesired β-hydride elimination.